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61.
Friedrich Kreyenschmidt Selim E. Meurer Prof. Dr. Konrad Koszinowski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(23):5912-5921
>The combination of CoCl2 with bidentate phosphines is known to catalyze challenging cross-coupling and Heck-type reactions, but the mechanisms of these valuable transformations have not been established. Here, we use electrospray-ionization mass spectrometry to intercept the species formed in these reactions. Our results indicate that a sequence of transmetalation, reductive elimination, and redox disproportionation convert the cobalt(II) precatalyst into low-valent cobalt complexes. These species readily transfer single electrons to alkyl bromides, which thereupon dissociate into alkyl radicals and Br−. In cross-coupling reactions, the alkyl radicals add to the cobalt catalyst to form observable heteroleptic complexes, which release the coupling products through reductive eliminations. In the Heck-type reactions, the low abundance of newly formed ionic species renders the analysis more difficult. Nonetheless, our results also point to the occurrence of single-electron transfer processes and the involvement of radicals in these transformations. 相似文献
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Kamila Rybczyska-Tkaczyk Teresa Korniowicz-Kowalska Konrad A. Szychowski 《Molecules (Basel, Switzerland)》2021,26(2)
The aim of this study was to evaluate the bioremoval mechanism of anthracycline antibiotics by the white-rot fungus B. adusta CCBAS 930. The activity of oxidoreductases and levels of phenolic compounds and free radicals were determined during the biotransformation of anthraquinone antibiotics: daunomycin (DNR) and doxorubicin (DOX) by B. adusta strain CCBAS 930. Moreover, phytotoxicity (Lepidium sativum L.), ecotoxicity (Vibrio fischeri), genotoxicity and cytotoxicity of anthraquinone dyes were evaluated before and after biological treatment. More than 80% and 90% of DNR and DOX were removed by biodegradation (decolorization). Initial solutions of DNR and DOX were characterized by eco-, phyto-, geno- and cytotoxicity. Despite efficient decolorization, secondary metabolites, toxic to bacteria, formed during biotransformation of anthracycline antibiotics in B. adusta CCBAS 930 cultures. DNR and DOX metabolites did not increase reactive oxygen species (ROS) production in human fibroblasts and resazurin reduction. DNR metabolites did not change caspase-3 activity. 相似文献
65.
Gated Channels and Selectivity Tuning of CO2 over N2 Sorption by Post‐Synthetic Modification of a UiO‐66‐Type Metal–Organic Framework
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Alexander Kronast Sebastian Eckstein Dr. Peter T. Altenbuchner Dr. Konrad Hindelang Dr. Sergei I. Vagin Prof. Dr. Bernhard Rieger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(36):12800-12807
The highly porous and stable metal–organic framework (MOF) UiO‐66 was altered using post‐synthetic modifications (PSMs). Prefunctionalization allowed the introduction of carbon double bonds into the framework through a four‐step synthesis from 2‐bromo‐1,4‐benzenedicarboxylic acid; the organic linker 2‐allyl‐1,4‐benzenedicarboxylic acid was obtained. The corresponding functionalized MOF (UiO‐66‐allyl) served as a platform for further PSMs. From UiO‐66‐allyl, epoxy, dibromide, thioether, diamine, and amino alcohol functionalities were synthesized. The abilities of these compounds to adsorb CO2 and N2 were compared, which revealed the structure–selectivity correlations. All synthesized MOFs showed profound thermal stability together with an increased ability for selective CO2 uptake and molecular gate functionalities at low temperatures. 相似文献
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Association and Dissociation of Grignard Reagents RMgCl and Their Turbo Variant RMgCl⋅LiCl
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Christoph Schnegelsberg Sebastian Bachmann Marlene Kolter Thomas Auth Dr. Michael John Prof. Dr. Dietmar Stalke Prof. Dr. Konrad Koszinowski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(23):7752-7762
Grignard reagents RMgCl and their so‐called turbo variant, the highly reactive RMgCl?LiCl, are of exceptional synthetic utility. Nevertheless, it is still not fully understood which species these compounds form in solution and, in particular, in which way LiCl exerts its reactivity‐enhancing effect. A combination of electrospray‐ionization mass spectrometry, electrical conductivity measurements, NMR spectroscopy (including diffusion‐ordered spectroscopy), and quantum chemical calculations is used to analyze solutions of RMgCl (R=Me, Et, Bu, Hex, Oct, Dec, iPr, tBu, Ph) in tetrahydrofuran and other ethereal solvents in the absence and presence of stoichiometric amounts of LiCl. In tetrahydrofuran, RMgCl forms mononuclear species, which are converted into trinuclear anions as a result of the concentration increase experienced during the electrospray process. These trinuclear anions are theoretically predicted to adopt open cubic geometries, which remarkably resemble structural motifs previously found in the solid state. The molecular constituents of RMgCl and RMgCl?LiCl are interrelated via Schlenk equilibria and fast intermolecular exchange processes. A small portion of the Grignard reagent also forms anionic ate complexes in solution. The abundance of these more electron‐rich and hence supposedly more nucleophilic ate complexes strongly increases upon the addition of LiCl, thus rationalizing its beneficial effect on the reactivity of Grignard reagents. 相似文献
69.
Konrad Eichhorn Colombo Vladislav V. Kharton Alexandre P. Viskup Andrei V. Kovalevsky Aliaksandr L. Shaula Olav Bolland 《Journal of Solid State Electrochemistry》2011,15(2):329-347
A gas turbine power plant for CO2 capture, based on oxygen-permeable membranes with mixed ionic-electronic conductivity, was analysed with respect to long-term
stability by means of numerical simulation. Due to the attractive transport and physicochemical properties of mixed-conducting
La2NiO4+δ, this nickelate was selected as a prototype membrane material for this application. Experiments showed very slow degradation
of La2NiO4+δ membranes at oxygen chemical potentials close to atmospheric conditions, which are associated with kinetic demixing and other
microstructure-related factors. Interaction with CO2 in the intermediate temperature range also leads to lower oxygen permeation, whilst increasing oxygen pressure may cause
partial phase decomposition and microstructural changes, thus again limiting the range of possible operation conditions. The
relevant operational constraints were included in a detailed membrane-based gas turbine power plant model. The membrane performance
degradation with time was approximated by a linear function with average rate of 3.3% per 1,000 operation hours. Furthermore,
performance deterioration of the gas turbine compressor and turbine were also considered. Simulations revealed that the power
plant is substantially affected by degradation of the ceramic membranes and turbomachinery components. The already rather
small operating window was further narrowed when compared with a conventional gas turbine power plant. Two different designs
of the membrane-based power plant were analysed: (1) with and (2) without additional combustors (afterburners) between the
membrane reactor and the gas turbine. Afterburners increase thermal efficiency as well as power output, but also lead to non-negligible
CO2 emissions. In order to have a frame of comparison, results for a conventional gas turbine power plant with degradation of
turbomachinery components are also presented. Simulations representing changes in ambient temperature and fuel composition
as well as failure incidents were executed to analyse the susceptibility of the gas turbine power plant to external and internal
changes. 相似文献
70.
Angelika Baranowska-Łączkowska Berta Fernández Antonio Rizzo Filip Pawłowski 《Molecular physics》2015,113(13-14):1786-1793
Static and dynamic average polarisabilities and polarisability anisotropies of seven linear non-polar and polar molecules are calculated within the CCS, CC2, and CC3 approximations using a range of medium-sized basis sets: the polarised LPol-n (n = ds, dl, fs, fl), the aug-pc-n (n = 1, 2), the def2-SVPD, and -TZVPD basis sets. Reference values are obtained using a hierarchy of Dunning's (d-)aug-cc-pVXZ (X = D, T, Q, 5) basis sets. The results are discussed together with the available CCSD values in terms of basis set and correlation method errors, and their ratio. Detailed analysis shows that already the def2-SVPD basis set can be used in CCS polarisability calculations. When affordable, the slightly larger aug-pc-1 basis set is recommended, as it leads to significant reduction of basis set error. The def2-TZVPD, LPol-ds, and aug-pc-2 basis sets are optimal choice within the CC2 approximation, with the latter allowing to approach the CC2 basis set limit. The LPol-ds, -dl, and def2-TZVPD sets outperform the aug-cc-pVTZ set in average polarisability CCSD calculations, with the def2-TZVPD being competitive to other reduced-size sets also in determination of polarisability anisotropy. The aug-pc-2 basis is a particularly attractive choice for CCSD, giving the accuracy of aug-cc-pVQZ at a significantly reduced computational cost. The polarisability anisotropy is shown to be more computationally demanding than the average polarisability, in particular with respect to the accuracy of the correlation method and an accurate evaluation of this property requires at least the CCSD model. 相似文献