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71.
Es wird ein Berechnungsmodell für 2-Fluid-Strömungen mit drehendem Starrkörper vorgestellt, mit dem eine numerische Analyse der Strömungsvorgänge innerhalb von Schaufelwasserrädern möglich ist. Mit dem vorgestellten Berechnungsmodell erfolgt die erstmalige numerische Untersuchung der bei Schaufelwasserrädern auftretenden Strömungsvorgänge. Dabei werden die wesentlichen Punkte im Rahmen der numerischen Umsetzung eingehend diskutiert und die gewonnenen Ergebnisse anhand experimenteller Daten auf ihre physikalische Plausibilität hin überprüft. (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
72.
Here, we present a fast and simple hydrogen peroxide assay that is based on time-resolved fluorescence. The emission intensity of a complex consisting of terbium ions (Tb3+) and phthalic acid (PA) in HEPES buffer is quenched in the presence of H2O2 and this quenching is concentration-dependent. The novel PATb assay detects hydrogen peroxide at a pH range from 7.5 to 8.5 and with a detection limit of 150 nmol L−1 at pH 8.5. The total assay time is less than 1 min. The linear range of the assay can be adapted by a pH adjustment of the aqueous buffer and covers a concentration range from 310 nmol L−1 to 2.56 mmol L−1 in total which encompasses four orders of magnitude. The assay is compatible with high concentrations of all 47 tested inorganic and organic compounds. The PATb assay was applied to quantify H2O2 in polluted river water samples. In conclusion, this fast and easy-to-use assay detects H2O2 with high sensitivity and precision. 相似文献
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75.
Dr. Rüdiger W. Seidel Richard Goddard Constantin Hoch Iris M. Oppel 《无机化学与普通化学杂志》2011,637(11):1545-1554
Attempts to crystal engineer metallosupramolecularcomplexes from Cu(phen)2+ building blocks and the prototypical,rod‐like, exo‐bidentate ligand 4,4′‐bipyridine (4,4′‐bipy) by layering techniques are described. Reactions of Cu(phen)2+ (phen = 1,10‐phenanthroline) with 4,4′‐bipy in the presence of NO3– counterions yielded two distinct, discrete, dinuclear, Ci symmetric, dumbbell‐typecomplexes, [{Cu(NO3)2(phen)}2(4,4′‐bipy)] ( 1 ) and [{Cu(NO3)(phen)(H2O)}2(4,4′‐bipy)](NO3)2 ( 2 ), depending upon the mixture of solvents used for crystallization. In compound 1 , a mono‐ and a bidentate nitrato group coordinate to Cu2+, whereas in 2 the monodentate nitrato groups are replaced by aqua ligands, which introduce additional hydrogen‐bond donor functionality to the molecule. The crystal structure of 1 was determined by single‐crystal X‐ray analysis at 296 and 110 K. Upon cooling, a disorder‐order transition occurs, with retention of the space group symmetry. The crystal structure of 2 at room temperature was reported previously [Z.‐X. Du, J.‐X. Li, Acta Cryst. 2007 , E63, m2282]. We have redetermined the crystal structure of 2 at 100 K. A phase transition is not observed for 2 , but the low temperature single‐crystal structure determination is of significantly higher precision than the room temperature study. Both 1 and 2 are obtained phase‐pure, as proven by powder X‐ray diffraction of the bulk materials. Crystals of [Cu(phen)(CF3SO3)2(4,4′‐bipy) · 0.5H2O]n ( 3 ), a one‐dimensional coordination polymer, were obtained from [Cu(CF3SO3)2(phen)(H2O)2] and 4,4′‐bipy. In 3 , Cu(phen)2+ corner units are joined by 4,4′‐bipy via the two vacant cis sites to form polymeric zig‐zag chains, which are tightly packed in the crystal. Compounds 1 – 3 were further studied by infrared spectroscopy. 相似文献
76.
Sindbert S Kalinin S Nguyen H Kienzler A Clima L Bannwarth W Appel B Müller S Seidel CA 《Journal of the American Chemical Society》2011,133(8):2463-2480
In Fo?rster resonance energy transfer (FRET) experiments, the donor (D) and acceptor (A) fluorophores are usually attached to the macromolecule of interest via long flexible linkers of up to 15 ? in length. This causes significant uncertainties in quantitative distance measurements and prevents experiments with short distances between the attachment points of the dyes due to possible dye-dye interactions. We present two approaches to overcome the above problems as demonstrated by FRET measurements for a series of dsDNA and dsRNA internally labeled with Alexa488 and Cy5 as D and A dye, respectively. First, we characterize the influence of linker length and flexibility on FRET for different dye linker types (long, intermediate, short) by analyzing fluorescence lifetime and anisotropy decays. For long linkers, we describe a straightforward procedure that allows for very high accuracy of FRET-based structure determination through proper consideration of the position distribution of the dye and of linker dynamics. The position distribution can be quickly calculated with geometric accessible volume (AV) simulations, provided that the local structure of RNA or DNA in the proximity of the dye is known and that the dye diffuses freely in the sterically allowed space. The AV approach provides results similar to molecular dynamics simulations (MD) and is fully consistent with experimental FRET data. In a benchmark study for ds A-RNA, an rmsd value of 1.3 ? is achieved. Considering the case of undefined dye environments or very short DA distances, we introduce short linkers with a propargyl or alkenyl unit for internal labeling of nucleic acids to minimize position uncertainties. Studies by ensemble time correlated single photon counting and single-molecule detection show that the nature of the linker strongly affects the radius of the dye's accessible volume (6-16 ?). For short propargyl linkers, heterogeneous dye environments are observed on the millisecond time scale. A detailed analysis of possible orientation effects (κ(2) problem) indicates that, for short linkers and unknown local environments, additional κ(2)-related uncertainties are clearly outweighed by better defined dye positions. 相似文献
77.
Thürmer S Seidel R Eberhardt W Bradforth SE Winter B 《Journal of the American Chemical Society》2011,133(32):12528-12535
We report here on the electron binding energies and ultrafast electronic relaxation of the Fe(3+)(aq) complex in FeCl(3) aqueous solution as measured by soft X-ray photoelectron (PE) spectroscopy from a vacuum liquid microjet. Covalent mixing between the 3d valence orbitals of the iron cation and the molecular orbitals of water in the ground-state solution is directly revealed by spectroscopy of the highest partially occupied molecular orbitals. Valence PE spectra, obtained for photon energies near the iron 2p absorption edge, exhibit large resonant enhancements. These resonant PE features identify 3d-O2p transient hybridization between iron and water-derived orbitals and are an indication of charge transfer within the electronically excited Fe(3+)(aq)* complex. Charge transfer from water to iron is also revealed by the 2p core-level PE spectrum, and the asymmetric peak shape additionally identifies the characteristic multiplet interactions in the 2p core-hole state. The electronic structure of water molecules in the first hydration shell is selectively probed by Auger decay from water molecules, at excitation energies well below the O1s absorption edge of neat water. These experiments lay the groundwork for establishing resonant PE spectroscopy for the study of electronic-structure dynamics in the large family of transition metal (aqueous) solutions. 相似文献
78.
Bollermann T Schwedler I Molon M Freitag K Gemel C Seidel RW Fischer RA 《Dalton transactions (Cambridge, England : 2003)》2011,40(46):12570-12577
The reactions of heteroleptic GaCp*/CO containing transition metal complexes of iron and cobalt, namely [(CO)(3)M(μ(2)-GaCp*)(m)M(CO)(3)] (Cp* = pentamethylcyclopentadienyl; M = Fe, m = 3; M = Co, m = 2) and [Fe(CO)(4)(GaCp*)], with ZnMe(2) in toluene and the presence of a coordinating co-solvent were investigated. The reaction of the iron complex [Fe(CO)(4)(GaCp*)] with ZnMe(2) in presence of tetrahydrofurane (thf) leads to the dimeric compound [(CO)(4)Fe{μ(2)-Zn(thf)(2)}(2)Fe(CO)(4)] (1). Reaction of [(CO)(3)Fe(μ(2)-GaCp*(3))Fe(CO)(3)] with ZnMe(2) and stoichiometric amounts of thf leads to the formation of [(CO)(3)Fe{μ(2)-Zn(thf)(2)}(2)(μ(2)-ZnMe)(2)Fe(CO)(3)] (2) containing {Zn(thf)(2)} as well as ZnMe ligands. Using pyridine (py) instead of thf leads to [(CO)(3)Fe{μ(2)-Zn(py)(2)}(3)Fe(CO)(3)] (3) via replacement of all GaCp* ligands by three{Zn(py)(2)} groups. In contrast, reaction of [(CO)(3)Co(μ(2)-GaCp*)(2)Co(CO)(3)] with ZnMe(2) in the presence of py or thf leads in both cases to the formation of [(CO)(3)Co{μ(2)-ZnL(2)}(μ(2)-ZnCp*)(2)Co(CO)(3)] (L = py (4), thf (5)) via replacement of GaCp* with {Zn(L)(2)} units as well as Cp* transfer from the gallium to the zinc centre. All compounds were characterised by NMR spectroscopy, IR spectroscopy, single crystal X-ray diffraction and elemental analysis. 相似文献
79.
Redox isomerization via azomethine ylide intermediates: N-alkyl indoles from indolines and aldehydes
Indolines react with aromatic and heteroaromatic aldehydes to yield N-alkyl indoles in a benzoic acid catalyzed redox isomerization reaction. Azomethine ylides are intermediates in this process which was established by intramolecular [3 + 2] trapping experiments. 相似文献
80.
α-Amino acids react with aldehydes in the presence of a cyanide source to form α-amino nitriles in what can be considered a decarboxylative variant of the classical Strecker reaction. This unprecedented transformation does not require the use of a metal catalyst and provides facile access to valuable α-amino nitriles that are inaccessible by traditional Strecker chemistry. 相似文献