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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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Aleksandra Stegliska Anastasiia Bekhter Pawe Wawrzyniak Alina Kunicka-Styczyska Konrad Jastrzbek Micha Fidler Krzysztof
migielski Beata Gutarowska 《Molecules (Basel, Switzerland)》2022,27(5)
The purpose of the study was to select an environmentally friendly plant biopesticide to protect seed potatoes against phytopathogens. The scope included the evaluation of the antimicrobial activities of 22 plant water extracts, 22 water-glycol extracts, and 3 subcritical carbon dioxide extracts using the agar diffusion method against 10 potato phytopathogens. For the most effective extracts, minimal inhibitory concentration (MIC), chemical composition analysis by gas chromatography–mass spectrometry and in situ assays on seed potatoes were performed. Garlic water extract was finally selected as the most effective in phytopathogen growth inhibition, both in vitro and in situ, with MIC values ranging between 6.3–25 mg/mL. 5-Hydroxymethylfurfural was determined to be the main component of this extract (33.24%). Garlic water extract was proposed as a potential biopesticide against potato phytopathogens. 相似文献
65.
The anionic polymerization of butadiene, to both the 1,2- and 1,4-addition products, is an important industrial process. It is known that the reaction can be steered to either the 1,2- or 1,4-product by the addition, or absence, of a complexing solvent such as ether. The goals of the current study were to map the MNDO Potential Energy Surfaces (PES) of the propagation reactions both in the presence and absence of dimethyl ether to gain insight into the factors influencing the reaction's selectivity. Single point ab initio calculations at the DZP level were run on all reactants, products and transition states as a cross check on the MNDO results. 相似文献
66.
Konrad Skotnicki Ireneusz Janik Klaudia Sadowska Grazyna Leszczynska Krzysztof Bobrowski 《Molecules (Basel, Switzerland)》2022,27(1)
One-electron oxidation of 2-selenouracil (2-SeU) by hydroxyl (●OH) and azide (●N3) radicals leads to various primary reactive intermediates. Their optical absorption spectra and kinetic characteristics were studied by pulse radiolysis with UV-vis spectrophotometric and conductivity detection and by the density functional theory (DFT) method. The transient absorption spectra recorded in the reactions of ●OH with 2-SeU are dominated by an absorption band with an λmax = 440 nm, the intensity of which depends on the concentration of 2-SeU and pH. Based on the combination of conductometric and DFT studies, the transient absorption band observed both at low and high concentrations of 2-SeU was assigned to the dimeric 2c-3e Se-Se-bonded radical in neutral form (2●). The dimeric radical (2●) is formed in the reaction of a selenyl-type radical (6●) with 2-SeU, and both radicals are in equilibrium with Keq = 1.3 × 104 M−1 at pH 4 (below the pKa of 2-SeU). Similar equilibrium with Keq = 4.4 × 103 M−1 was determined for pH 10 (above the pKa of 2-SeU), which admittedly involves the same radical (6●) but with a dimeric 2c-3e Se-Se bonded radical in anionic form (2●−). In turn, at the lowest concentration of 2-SeU (0.05 mM) and pH 10, the transient absorption spectrum is dominated by an absorption band with an λmax = 390 nm, which was assigned to the ●OH adduct to the double bond at C5 carbon atom (3●) based on DFT calculations. Similar spectral and kinetic features were also observed during the ●N3-induced oxidation of 2-SeU. In principle, our results mostly revealed similarities in one-electron oxidation pathways of 2-SeU and 2-thiouracil (2-TU). The major difference concerns the stability of dimeric radicals with a 2c-3e chalcogen-chalcogen bond in favor of 2-SeU. 相似文献
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69.
Ernest Z. Manson Kyama C. Mutinda Joseph K. Gikunju Aleksandra Bocian Konrad K. Hus Vladimír Petrílla Jaroslav Legth James H. Kimotho 《Molecules (Basel, Switzerland)》2022,27(3)
The administration of toxin-specific therapy in snake envenoming is predicated on improved diagnostic techniques capable of detecting specific venom toxins. Various serological tests have been used in detecting snakebite envenoming. Comparatively, enzyme-linked immunosorbent assay (ELISA) has been shown to offer a wider practical application. We report an inhibition ELISA for detecting three-finger toxin (3FTx) proteins in venoms of African spitting cobras. The optimized assay detected 3FTxs in N. ashei (including other Naja sp.) venoms, spiked samples, and venom-challenged mice samples. In venoms of Naja sp., the assay showed inhibition, implying the detection of 3FTxs, but showed little or no inhibition in non-Naja sp. In mice-spiked samples, one-way ANOVA results showed that the observed inhibition was not statistically significant between spiked samples and negative control (p-value = 0.164). Similarly, the observed differences in inhibition between venom-challenged and negative control samples were not statistically significant (p-value = 0.9109). At an LOD of 0.01 µg/mL, the assay was able to confirm the presence of 3FTxs in the samples. Our results show a proof of concept for the use of an inhibition ELISA model as a tool for detecting 3FTxs in the venoms of African spitting cobra snakes. 相似文献
70.
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