No abstract

Ataxia telangiectasia (AT) is a pleiotropic genetic disorder characterized by progressive neurodegeneration, especially of cerebellar Purkinje cells, immunodeficiency, increased incidence of cancer, and premature aging. The disease is caused by functional inactivation of the ATM (AT-mutated) gene product, which is thought to act as a sensor of reactive oxygen species and oxidative damage of cellular macromolecules and DNA. The compound phenotype of AT might thus be linked to a continuous state of oxidative stress leading to an increase of programmed cell death (apoptosis). To assess this hypothesis, we analyzed lipid peroxidation products and the oxidative stress associated DNA base damage 8-hydroxy-2-deoxyguanosine in patients with AT. Oxidative damage to lipids and DNA was found to be markedly increased in AT patients. These results indicate that ATM might play an important role in the maintenance of cell homeostasis in response to oxidative damage. In this context, a better control of levels of reactive oxygen species could be a rational foundation of therapeutic intervention to help alleviate some of the symptoms associated with AT.

A new Ru oligomer of formula {[Ru II (bda-κ-N 2 O 2 )(4,4′-bpy)] 10 (4,4′-bpy)}, 10 (bda is [2,2′-bipyridine]-6,6′-dicarboxylate and 4,4′-bpy is 4,4′-bipyridine), was synthesized and thoroughly characterized with spectroscopic, X-ray, and electrochemical techniques. This oligomer exhibits strong affinity for graphitic materials through CH−π interactions and thus easily anchors on multiwalled carbon nanotubes (CNT), generating the molecular hybrid material 10@CNT . The latter acts as a water oxidation catalyst and converts to a new species, 10′(H 2 O) 2 @CNT , during the electrochemical oxygen evolution process involving solvation and ligand reorganization facilitated by the interactions of molecular Ru catalyst and the surface. This heterogeneous system has been shown to be a powerful and robust molecular hybrid anode for electrocatalytic water oxidation into molecular oxygen, achieving current densities in the range of 200 mA/cm 2 at pH 7 under an applied potential of 1.45 V vs NHE. The remarkable long-term stability of this hybrid material during turnover is rationalized based on the supramolecular interaction of the catalyst with the graphitic surface.

Conformational changes induced by ligand substituents in macrocyclic Ru complexes strongly affect their chemical and photocatalytic efficiencies in water oxidation.

In recent years the interest of shape-persistent organic cage compounds synthesized by dynamic covalent chemistry (DCC) has risen, because these cages are potentially interesting for gas sorption or -separation. One such reaction in DCC is the condensation of boronic acids with diols to form boronic esters. Most interestingly, the variety of geometries and sizes for boronic ester cages is much lower than that of, for example, imine-based cages. Here, a small series of shape-persistent [4+6] tetrahedral boronic ester cages is introduced. One cage has a high specific surface area of 511 m g and selectively adsorbs ethane over ethylene and acetylene.

Catalytic water splitting is a viable process for the generation of renewable fuels. Here it is reported for the first time that a trinuclear supramolecular Ru(bda) (bda: 2,2′‐bipyridine‐6,6′‐dicarboxylate) catalyst, anchored on multi‐walled carbon nanotubes and subsequently immobilized on glassy carbon electrodes, shows outstanding performance in heterogeneous water oxidation. Activation of the catalyst on anodes by repetitive cyclic voltammetry (CV) scans results in a catalytic current density of 186 mA cm−2 at a potential of 1.45 V versus NHE. The activated catalyst performs water oxidation at an onset overpotential of 330 mV. The remarkably high stability of the hybrid anode is demonstrated by X‐ray absorption spectroscopy and electrochemically, revealing the absence of any degradation after 1.8 million turnovers. Foot of the wave analysis of CV data of activated electrodes with different concentrations of catalyst indicates a monomolecular water nucleophilic attack mechanism with an apparent rate constant of TOFmax (turnover frequency) of 3200 s−1.

No abstract

Two di-and tetranuclear Ru(bda) (bda: 2,2'-bipyridine-6,6'-dicarboxylate) macrocyclic complexes were synthesized and their catalytic activities in chemical and photochemical water oxidation investigated in a comparative manner to our previously reported trinuclear congener. Our studies have shown that the catalytic activities of this homologous series of multinuclear Ru(bda) macrocycles in homogeneous water oxidation are dependent on their size, exhibiting highest efficiencies for the largest tetranuclear catalyst. The turnover frequencies (TOFs) have increased from di-to tetranuclear macrocycles not only per catalyst molecule but more importantly also per Ru unit with TOF of 6 s À 1 to 8.7 s À 1 and 10.5 s À 1 in chemical and 0.6 s À 1 to 3.3 s À 1 and 5.8 s À 1 in photochemical water oxidation per Ru unit, respectively. Thus, for the first time, a clear structure-activity relationship could be established for this novel class of macrocyclic water oxidation catalysts.