Photo-triggered hydrogen atom transfer from an iridium hydride complex to unactivated olefins

Many photoactive metal complexes can act as electron donors or acceptors upon photoexcitation, but hydrogen atom transfer (HAT) reactivity is rare. We discovered that a typical representative of a widely used class of iridium hydride complexes acts as an H-atom donor to unactivated olefins upon irradiation at 470 nm in the presence of tertiary alkyl amines as sacrificial electron and proton sources. The catalytic hydrogenation of simple olefins served as a test ground to establish this new photo-reactivity of iridium hydrides. Substrates that are very difficult to activate by photoinduced electron transfer were readily hydrogenated, and structure–reactivity relationships established with 12 different olefins are in line with typical HAT reactivity, reflecting the relative stabilities of radical intermediates formed by HAT. Radical clock, H/D isotope labeling, and transient absorption experiments provide further mechanistic insight and corroborate the interpretation of the overall reactivity in terms of photo-triggered hydrogen atom transfer (photo-HAT). The catalytically active species is identified as an Ir(ii) hydride with an Ir^II–H bond dissociation free energy around 44 kcal mol⁻¹, which is formed after reductive ³MLCT excited-state quenching of the corresponding Ir(iii) hydride, i.e. the actual HAT step occurs on the ground-state potential energy surface. The photo-HAT reactivity presented here represents a conceptually novel approach to photocatalysis with metal complexes, which is fundamentally different from the many prior studies relying on photoinduced electron transfer.

Upon irradiation with visible light, an iridium hydride complex undergoes hydrogen atom transfer (HAT) to unactivated olefins in presence of a sacrificial electron donor and a proton source.     

Design, synthesis, and evaluation of a biomimetic artificial photolyase model

Two new artificial photolyase models that recognize pyrimidine dimers in protic and aprotic organic solvents as well as in water through a combination of charge and hydrogen-bonding interactions and use a mimic of the flavine to achieve repair through reductive photoinduced electron transfer are presented. Fluorescence and NMR titration studies show that it forms a 1:1 complex with pyrimidine dimers with binding constants of approximately 10(3) M(-1) in acetonitrile or methanol, while binding constants in water at pH 7.2 are slightly lower. Excitation of the complex with visible light leads to clean and rapid cycloreversion of the pyrimidine dimer through photoinduced electron transfer catalysis. The reaction in water is significantly faster than in organic solvents. The reaction slows down at higher conversions due to product inhibition.     

Determining elemental strontium distribution in rat bones treated with strontium ranelate and strontium citrate using 2D micro-XRF and 3D dual energy K-edge subtraction synchrotron imaging

Strontium-based medications, such as strontium ranelate, have been suggested to have therapeutic effects in patients with osteoporosis. Strontium salts available off-shelf in stores across North America are assumed to provide similar effects as strontium ranelate and thus should lead to similar distributions of elemental strontium incorporated in bone. The objective of this study was to compare the spatial distribution of strontium in animal bones following the administration of strontium ranelate and strontium citrate. Seventeen-week-old Sprague–Dawley rats were split into three groups over 10 weeks and given 625 mg/kg/day of strontium ranelate and 676 mg/kg/day of strontium citrate; the control group received no additional supplementary strontium. The humeri were collected from all animals, and strontium distribution was mapped using 2D micro-XRF and 3D dual energy K-edge subtraction (KES) imaging. 2D and 3D elemental mapping methods demonstrated that strontium delivered during treatment by both salts had the same spatial distribution. 3D elemental strontium maps of treated animal bones showed that strontium was largely observed in the trabecular regions under the epiphyseal (growth) plate. The thickness of the strontium layers in both the strontium ranelate and strontium citrate sample was not significantly different (p = .9201). 2D micro-XRF and 3D dual-energy KES images effectively elucidated the spatial distribution of elemental strontium in calcified tissue. These methods provide a novel approach to evaluating the potential efficacy of strontium supplements in the treatment of osteoporosis.     

PEROXIDASE INDUCED CHEMILUMINESCENCE IN THE OXIDATION OF PYROGALLOL AND PURPUROGALLIN. INFLUENCE OF AZIDE

Abstract— The chemiluminescence (CL) emitted during the peroxidase catalyzed oxidation of purpurogallin and pyrogallol depends on one and two molecules of enzyme, respectively. Using microperoxidase, CL with purpurogallin also depends on two molecules of enzyme (above 0.3 μ M enzyme). Sodium azide inhibits the CL emitted by all reactions depending on two molecules of enzyme but enhances the CL of reactions depending on one molecule of peroxidase (purpurogallin + 0.75 n M horseradish peroxidase). The formation of functional enzyme dimols during the oxidative process is discussed.     

Isolation of swinholide A and related glycosylated derivatives from two field collections of marine cyanobacteria

[structure: see text] Chemical investigation of two field collections of marine cyanobacteria has led to the discovery of two new cytotoxic natural products, ankaraholides A (2) and B (3), along with the known compound swinholide A (1). Since swinholide-type compounds were previously localized to the heterotrophic bacteria of sponges, these findings raise intriguing questions about their true metabolic source.