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.     

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.     

Receiving beam patterns in the horizontal plane of a harbor porpoise (Phocoena phocoena)

Receiving beam patterns of a harbor porpoise were measured in the horizontal plane, using narrow-band frequency modulated signals with center frequencies of 16, 64, and 100 kHz. Total signal duration was 1000 ms, including a 200 ms rise time and 300 ms fall time. The harbor porpoise was trained to participate in a psychophysical test and stationed itself horizontally in a specific direction in the center of a 16-m-diameter circle consisting of 16 equally-spaced underwater transducers. The animal's head and the transducers were in the same horizontal plane, 1.5 m below the water surface. The go/no-go response paradigm was used; the animal left the listening station when it heard a sound signal. The method of constants was applied. For each transducer the 50% detection threshold amplitude was determined in 16 trials per amplitude, for each of the three frequencies. The beam patterns were not symmetrical with respect to the midline of the animal's body, but had a deflection of 3-7 degrees to the right. The receiving beam pattern narrowed with increasing frequency. Assuming that the pattern is rotation-symmetrical according to an average of the horizontal beam pattern halves, the receiving directivity indices are 4.3 at 16 kHz, 6.0 at 64 kHz, and 11.7 dB at 100 kHz. The receiving directivity indices of the porpoise were lower than those measured for bottlenose dolphins. This means that harbor porpoises have wider receiving beam patterns than bottlenose dolphins for the same frequencies. Directivity of hearing improves the signal-to-noise ratio and thus is a tool for a better detection of certain signals in a given ambient noise condition.