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61.
Martin Heise Bertold Rasche Dr. Anna Isaeva Dr. Alexey I. Baranov Prof. Dr. Michael Ruck Konrad Schäfer Prof. Dr. Rainer Pöttgen Jens‐Peter Eufinger Prof. Dr. Jürgen Janek 《Angewandte Chemie (International ed. in English)》2014,53(28):7344-7348
Nanoparticles of Bi3Ir, obtained from a microwave‐assisted polyol process, activate molecular oxygen from air at room temperature and reversibly intercalate it as oxide ions. The closely related structures of Bi3Ir and Bi3IrOx (x≤2) were investigated by X‐ray diffraction, electron microscopy, and quantum‐chemical modeling. In the topochemically formed metallic suboxide, the intermetallic building units are fully preserved. Time‐ and temperature‐dependent monitoring of the oxygen uptake in an oxygen‐filled chamber shows that the activation energy for oxide diffusion (84 meV) is one order of magnitude smaller than that in any known material. Bi3IrOx is the first metallic oxide ion conductor and also the first that operates at room temperature. 相似文献
62.
Dr. Marlene Kolter Prof. Dr. Konrad Koszinowski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(53):12212-12218
The electron-poor palladium(0) complex L3Pd (L=tris[3,5-bis(trifluoromethyl)phenyl]phosphine) reacts with Grignard reagents RMgX and organolithium compounds RLi via transmetalation to furnish the anionic organopalladates [L2PdR]−, as shown by negative-ion mode electrospray-ionization mass spectrometry. These palladates undergo oxidative additions of organyl halides R′X (or related SN2-type reactions) followed by further transmetalation. Gas-phase fragmentation of the resulting heteroleptic palladate(II) complexes results in the reductive elimination of the cross-coupling products RR′. This reaction sequence corresponds to a catalytic cycle, in which the order of the elementary steps of transmetalation and oxidative addition is switched relative to that of palladium-catalyzed cross-coupling reactions proceeding via neutral intermediates. An attractive feature of the palladate-based catalytic system is its ability to mediate challenging alkyl–alkyl coupling reactions. However, the poor stability of the phosphine ligand L against decomposition reactions has so far prevented its successful use in practical applications. 相似文献
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Christiane Lorenz Harald Hagendorfer Natalie von Goetz Ralf Kaegi Robert Gehrig Andrea Ulrich Martin Scheringer Konrad Hungerbühler 《Journal of nanoparticle research》2011,13(8):3377-3391
Consumer spray products are already on the market in the cosmetics and household sector, which suggest by their label that
they contain engineered nanoparticles (ENP). Sprays are considered critical for human health, because the lungs represent
a major route for the uptake of ENP into the human body. To contribute to the exposure assessment of ENP in consumer spray
products, we analyzed ENP in four commercially available sprays: one antiperspirant, two shoe impregnation sprays, and one
plant-strengthening agent. The spray dispersions were analyzed by inductively coupled plasma mass spectrometry (ICPMS) and
(scanning-) transmission electron microscopy ((S)TEM). Aerosols were generated by using the original vessels, and analyzed
by scanning mobility particle sizer (SMPS) and (S)TEM. On the basis of SMPS results, the nanosized aerosol depositing in the
respiratory tract was modeled for female and male consumers. The derived exposure levels reflect a single spray application.
We identified ENP in the dispersions of two products (shoe impregnation and plant spray). Nanosized aerosols were observed
in three products that contained propellant gas. The aerosol number concentration increased linearly with the sprayed amount,
with the highest concentration resulting from the antiperspirant. Modeled aerosol exposure levels were in the range of 1010 nanosized aerosol components per person and application event for the antiperspirant and the impregnation sprays, with the
largest fraction of nanosized aerosol depositing in the alveolar region. Negligible exposure from the application of the plant
spray (pump spray) was observed. 相似文献
65.
Sebastian Weske Ramona Schoop Prof. Dr. Konrad Koszinowski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(32):11310-11316
Trifluoromethylation reactions have recently received increased attention because of the beneficial effect of the trifluoromethyl group on the pharmacological properties of numerous substances. A common method to introduce the trifluoromethyl group employs the Ruppert–Prakash reagent, that is, Si(CH3)3CF3, together with a copper(I) halide. We have applied this method to the trifluoromethylation of aromatic alkynes and used electrospray‐ionization mass spectrometry to investigate the mechanism of these reactions in tetrahydrofuran, dichloromethane, and acetonitrile as well as with and without added 1,10‐phenanthroline. In the absence of the alkyne component, the homoleptic ate complexes [Cu(CF3)2]? and [Cu(CF3)4]? were observed. In the presence of the alkynes RH, the heteroleptic complexes [Cu(CF3)3R]? were detected as well. Upon gas‐phase fragmentation, these key intermediates released the cross‐coupling products R?CF3 with perfect selectivity. Apparently, the [Cu(CF3)3R]? complexes did not originate from homoleptic cuprate anions, but from unobservable neutral precursors. The present results moreover point to the involvement of oxygen as the oxidizing agent. 相似文献
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67.
Konrad J. Swanepoel 《Proceedings of the American Mathematical Society》1999,127(7):2155-2162
A hollow axis-aligned box is the boundary of the cartesian product of compact intervals in . We show that for , if any of a collection of hollow axis-aligned boxes have non-empty intersection, then the whole collection has non-empty intersection; and if any of a collection of hollow axis-aligned rectangles in have non-empty intersection, then the whole collection has non-empty intersection. The values for and for are the best possible in general. We also characterize the collections of hollow boxes which would be counterexamples if were lowered to , and to , respectively.
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