Search results for " oxygen"
showing 10 items of 1626 documents
First principles simulations on migration paths of oxygen interstitials in magnesium aluminate spinel
2018
This study has been carried out within the framework of the EURO fusion Consortium and has been provided funding from the Euratom research and training program 2014–2018 under grant agreement No. 633053. The authors are indebted to A.I. Popov, A.C. Lushchik and R. Vila for stimulating discussions. Technical assistance from O. Lisovski is appreciated too. The views and opinions expressed herein do not necessarily reflect those of the European Commission. Calculations have been performed using Marconi supercomputer system based in Italy at CINECA Supercomputing Centre.
Photochemically Produced Singlet Oxygen: Applications and Perspectives
2018
This Review aims to provide early stage researchers with an updated guide to applications of photochemically produced singlet oxygen and, at the same time, widen the experienced researcher's perspectives in a holistic approach to singlet oxygen chemistry. Without being exhaustive, literature between 2010 and early 2018 has been surveyed by focusing on a critical evaluation of new knowledge and applications. After an introductory section concerning singlet oxygen production, detection, and interactions with biological systems, subsequent sections describe current applications of singlet-oxygen-enabled technology. Besides strictly chemical synthesis applications, attention has been given to t…
Total Synthesis of (-)-Oxycodone via Anodic Aryl-Aryl Coupling.
2019
A fully regio- and diastereoselective electrochemical 4a–2′-coupling of a 3′,4′,5′-trioxygenated laudanosine derivative enables the synthesis of the corresponding morphinandienone. This key intermediate is further transformed into (−)-oxycodone through conjugate nucleophilic substitution for E-ring closure and [4 + 2] cycloaddition with photogenerated singlet oxygen to accomplish diastereoselective hydroxylation at C-14. The anodic transformation provides high yields and can be performed under constant current conditions both in a simple undivided cell or in continuous flow.
Effect of Iodination on the Photophysics of the Laser Borane anti-B18H22: Generation of Efficient Photosensitizers of Oxygen
2019
Treatment of the laser borane anti-B18H22 (compound 1) with iodine in ethanol gives the monoiodinated derivative 7-I-anti-B18H21 (compound 2) in 67% yield, or, by reaction with iodine or ICl in the presence of AlCl3 in dichloromethane, the diiodinated derivative 4,4'-I2-anti-B18H20 (compound 3) in 85% yield. On excitation with 360 nm light, both compounds 2 and 3 give strong green phosphorescent emissions (λmax = 525 nm, ΦL = 0.41 and λmax = 545 nm, ΦL = 0.71 respectively) that are quenched by dioxygen to produce O2(1Δg) singlet oxygen with quantum yields of ΦΔ = 0.52 and 0.36 respectively. Similarly strong emissions can be stimulated via the nonlinear process of two-photon absorption when …
Photo-Chromium: Sensitizer for Visible-Light-Induced Oxidative C−H Bond Functionalization-Electron or Energy Transfer?
2017
The chromium(III) sensitizer [Cr(ddpd)2]3+ - based on an earth-abundant metal center - possesses a unique excited state potential energy landscape (ddpd = N,N'-dimethyl-N,N'-dipyridine-2-ylpyridine-2,6-diamine). The very large energy gap between the redox active and substitutionally labile 4T2 state and the long-lived low-energy 2E spin-flip state enables a selective, efficient sensitization of triplet dioxygen to give singlet dioxygen. Ultrafast intersystem crossing after the Franck Condon point from the 4T2 to the 2E excited state within 3.5 ps precludes intermolecular electron transfer pathways from the ultrashort-lived excited 4T2 state. This specific excited state reactivity enables a …
Room-Temperature Phosphorescence and Efficient Singlet Oxygen Production by Cyclometalated Pt(II) Complexes with Aromatic Alkynyl Ligands
2020
The synthesis of five novel cyclometalated platinum(II) compounds containing five different alkynyl-chromophores was achieved by the reaction of the previously synthesized Pt–Cl cyclometalated compound (1) with the corresponding RC≡CH by a Sonogashira reaction. It was observed that the spectral and photophysical characteristics of the cyclometalated platinum(II) complexes (Pt–Ar) are essentially associated with the platinum-cyclometalated unit. Room-temperature emission of the Pt–Ar complexes was attributed to phosphorescence in agreement with DFT calculations. Broad nanosecond (ns)-transient absorption spectra were observed with decays approximately identical to those obtained from the emi…
Interpretation of the nitrogen isotopic composition of Precambrian sedimentary rocks: Assumptions and perspectives
2016
International audience; Nitrogen isotope compositions in sedimentary rocks (d(15)N(sed)) are routinely used for reconstructing Cenozoic N-biogeochemical cycling and are also being increasingly applied to understanding the evolution of ancient environments. Here we review the existing knowledge and rationale behind the use of d(15)N(sed) as a proxy for the Precambrian N-biogeochemical cycle with the aims of (i) identifying the major uncertainties that affect analyses and interpretation of nitrogen isotopes in ancient sedimentary rocks, (ii) developing a framework for interpreting the Precambrian d(15)N(sed) record, (iii) testing this framework against a database of Precambrian d(15)N(sed) va…
Reactive oxygen species formed in aqueous mixtures of secondary organic aerosols and mineral dust influencing cloud chemistry and public health in th…
2017
Mineral dust and secondary organic aerosols (SOA) account for a major fraction of atmospheric particulate matter, affecting climate, air quality and public health. How mineral dust interacts with SOA to influence cloud chemistry and public health, however, is not well understood. Here, we investigated the formation of reactive oxygen species (ROS), which are key species of atmospheric and physiological chemistry, in aqueous mixtures of SOA and mineral dust by applying electron paramagnetic resonance (EPR) spectrometry in combination with a spin-trapping technique, liquid chromatography-tandem mass spectrometry (LC-MS/MS), and a kinetic model. We found that substantial amounts of ROS includi…
Simulating speleothem growth in the laboratory: Determination of the stable isotope fractionation (δ13C and δ18O) between H2O, DIC and CaCO3
2019
Abstract Here we present novel cave-analogue experiments directly investigating stable carbon and oxygen isotope fractionation between the major involved species of the carbonate system (HCO3−, CO2, CaCO3 and H2O). In these experiments, which were performed under controlled conditions inside a climate box, a thin film of solution flew down an inclined marble or glass plate. After different distances of flow and, thus, residence times on the plate, pH, electrical conductivity, supersaturation with respect to calcite, precipitation rate as well as the δ18O and δ13C values of the dissolved inorganic carbon (DIC) and the precipitated CaCO3 were obtained. Progressive precipitation of CaCO3 along…
Oxygen isotope compositions of phosphate from arvicoline teeth and Quaternary climatic changes, Gigny, French Jura
2004
Oxygen isotope compositions of biogenic phosphates from mammals are widely used as proxies of the isotopic compositions of meteoric waters that are roughly linearly related to the air temperature at high- and mid-latitudes. An oxygen isotope fractionation equation was determined by using present-day European arvicoline (rodents) tooth phosphate: δ18Op = 20.98(±0.59) + 0.572(±0.065) δ18Ow. This fractionation equation was applied to the Late Pleistocene karstic sequence of Gigny, French Jura. Comparison between the oxygen isotope compositions of arvicoline tooth phosphate and Greenland ice core records suggests to reconsider the previously established hypothetical chronology of the sequence. …