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81.
Laura Senft Jamonica L. Moore Alicja Franke Katherine R. Fisher Andreas Scheitler Achim Zahl Ralph Puchta Dominik Fehn Sidney Ison Safaa Sader Ivana Ivanovi-Burmazovi Christian R. Goldsmith 《Chemical science》2021,12(31):10483
Reactivity assays previously suggested that two quinol-containing MRI contrast agent sensors for H2O2, [Mn(H2qp1)(MeCN)]2+ and [Mn(H4qp2)Br2], could also catalytically degrade superoxide. Subsequently, [Zn(H2qp1)(OTf)]+ was found to use the redox activity of the H2qp1 ligand to catalyze the conversion of O2˙− to O2 and H2O2, raising the possibility that the organic ligand, rather than the metal, could serve as the redox partner for O2˙− in the manganese chemistry. Here, we use stopped-flow kinetics and cryospray-ionization mass spectrometry (CSI-MS) analysis of the direct reactions between the manganese-containing contrast agents and O2˙− to confirm the activity and elucidate the catalytic mechanism. The obtained data are consistent with the operation of multiple parallel catalytic cycles, with both the quinol groups and manganese cycling through different oxidation states during the reactions with superoxide. The choice of ligand impacts the overall charges of the intermediates and allows us to visualize complementary sets of intermediates within the catalytic cycles using CSI-MS. With the diquinolic H4qp2, we detect Mn(iii)-superoxo intermediates with both reduced and oxidized forms of the ligand, a Mn(iii)-hydroperoxo compound, and what is formally a Mn(iv)-oxo species with the monoquinolate/mono-para-quinone form of H4qp2. With the monoquinolic H2qp1, we observe a Mn(ii)-superoxo ↔ Mn(iii)-peroxo intermediate with the oxidized para-quinone form of the ligand. The observation of these species suggests inner-sphere mechanisms for O2˙− oxidation and reduction that include both the ligand and manganese as redox partners. The higher positive charges of the complexes with the reduced and oxidized forms of H2qp1 compared to those with related forms of H4qp2 result in higher catalytic activity (kcat ∼ 108 M−1 s−1 at pH 7.4) that rivals those of the most active superoxide dismutase (SOD) mimics. The manganese complex with H2qp1 is markedly more stable in water than other highly active non-porphyrin-based and even some Mn(ii) porphyrin-based SOD mimics.Manganese complexes with polydentate quinol-containing ligands are found to catalyze the degradation of superoxide through inner-sphere mechanisms. The redox activity of the ligand stabilizes higher-valent manganese species. 相似文献
82.
Yanagisawa H Hengsberger M Leuenberger D Klöckner M Hafner C Greber T Osterwalder J 《Physical review letters》2011,107(8):087601
Energy distribution curves of laser-induced electron pulses from a tungsten tip have been measured as a function of tip voltage and laser power. Electron emission via tunneling through and/or excitation over the surface barrier from photoexcited nonequilibrium electron distributions are clearly observed. The spectral shapes largely vary with the emission processes and are strongly affected by electron dynamics. Simulations successfully reproduce the spectra, thus allowing direct insight into the involved electron dynamics and revealing the temporal tunability of electron emission via the two experimental parameters. These results should be useful to optimize the pulse characteristics for many applications based on ultrafast laser-induced electron emission. 相似文献
83.
The mechanism of the decomposition of acryloylcarbamates 7a–b yielding highly reactive isocyanates 3a–b was proposed based on NMR measurements and quantum chemical calculations. A good agreement between the experimental kinetic data and DFT calculations allowed us to demonstrate that the stability of 7a–d depends on the presence of methyl in the acryloyl moiety and the position of the nitro group in the nitrophenolic part of the molecule. Furthermore, the reactivity of 7a–d with weakly nucleophilic and sterically hindered 2,4,6‐tri‐tert‐butylaniline was explored by 1H NMR demonstrating the usefulness of reagents 7a–d offering access to a variety of 1‐N‐substituted uracils and thymines with potentially interesting biological properties. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
84.
Sheetal Saxena Alexander Summa Dominik Elsässer Michael Rüger Karl Mannheim 《The European Physical Journal C - Particles and Fields》2011,71(11):1815
As the largest mass concentrations in the local Universe, nearby clusters of galaxies and their central galaxies are prime
targets in searching for indirect signatures of dark matter annihilation (DMA). We seek to constrain the dark matter annihilation
emission component from multi-frequency observations of the central galaxy of the Virgo cluster. The annihilation emission
component is modeled by the prompt and inverse-Compton gamma rays from the hadronization of annihilation products from generic
weakly interacting dark matter particles. This component is fitted to the excess of the observed data above the spectral energy
distribution (SED) of the jet in M87, described with a best-fit synchrotron-self-Compton (SSC) spectrum. While this result
is not sufficiently significant to claim a detection, we emphasize that a dark matter “double hump signature” can be used
to unambiguously discriminate the dark matter emission component from the variable jet-related emission of M87 in future,
more extended observation campaigns. 相似文献
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Trushar Gohil Robert H. P. McGregor Dominik Szczerba Kathrin Burckhardt Krishnamurthy Muralidhar Gábor Székely 《国际流体数值方法杂志》2011,66(8):1037-1067
Cardiovascular diseases are one of the major causes of long‐term morbidity and mortality in human beings. The nearly epidemic increase in prevalence of such diseases poses a serious threat to public health and calls for efficient methods of diagnosis and treatment. Non‐invasive diagnostic procedures such as MRI are often used in this context; however, these are limited in terms of spatial and temporal resolution and do not provide information on time‐dependent pressures and wall shear stresses—key quantities considered to be partially responsible for the formation and development of related pathologies. The present study is concerned with the numerical simulation of oscillatory flow through the abdominal aortic bifurcation. Computational fluid dynamics simulation of oscillatory flow in a branched geometry at high Reynolds numbers poses considerable challenges. The present study reports a detailed comparison of simulations performed with a finite volume and a finite element method, two approaches with significant differences in their discretization strategy, treatment of boundary conditions and other numerical aspects. Both solvers were parallelized, using loop parallelization of the BiCGStab linear solver for the finite volume and domain decomposition based on the Schur complement method for the finite element technique. The experience gained with these two approaches for the solution of flow in a bifurcation forms the focus of this study. Although similar results were obtained for both methods, the computation time required for convergence was found to be significantly smaller for the finite element approach. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
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