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61.
Yannick Geiger Thierry Achard Aline Maisse-Franois Stphane Bellemin-Laponnaz 《Chemical science》2020,11(46):12453
The chiral ligand N-methylephedrine (NME) was found to catalyse the addition of dimethylzinc to benzaldehyde in an enantiodivergent way, with a monomeric and a homochiral dimeric complex both catalysing the reaction at a steady state and giving opposite product enantiomers. A change in the sign of the enantiomeric product was thus possible by simply varying the catalyst loading or the ligand ee, giving rise to an enantiodivergent non-linear effect. Simulations using a mathematical model confirmed the possibility of such behaviour and showed that this can lead to situations where a reaction gives racemic products, although the system is composed only of highly enantioselective individual catalysts. Furthermore, depending on the dimer''s degree of participation in the catalytic conversion, enantiodivergence may or may not be observed experimentally, which raises questions about the possibility of enantiodivergence in other monomer/dimer-catalysed systems. Simulations of the reaction kinetics showed that the observed kinetic constant kobs is highly dependent on user-controlled parameters, such as the catalyst concentration and the ligand ee, and may thus vary in a distinct way from one experimental setup to another. This unusual dependency of kobs allowed us to confirm that a previously observed U-shaped catalyst order vs. catalyst loading-plot is linked to the simultaneous catalytic activity of both monomeric and dimeric complexes.An asymmetric reaction consisting of competing monomeric and dimeric catalysts may explain enantiodivergent non-linear effects. 相似文献
62.
Dorin Geiger Hannes Lichte Martin Linck Michael Lehmann 《Microscopy and microanalysis》2008,14(1):68-81
Cs correctors have revolutionized transmission electron microscopy (TEM) in that they substantially improve point resolution and information limit. The object information is found sharply localized within 0.1 nm, and the intensity image can therefore be interpreted reliably on an atomic scale. However, for a conventional intensity image, the object exit wave can still not be detected completely in that the phase, and hence indispensable object information is missing. Therefore, for example, atomic electric-field distributions or magnetic domain structures cannot be accessed. Off-axis electron holography offers unique possibilities to recover completely the aberration-corrected object wave with uncorrected microscopes and hence we would not need a Cs-corrected microscope for improved lateral resolution. However, the performance of holography is affected by aberrations of the recording TEM in that the signal/noise properties ("phase detection limit") of the reconstructed wave are degraded. Therefore, we have realized off-axis electron holography with a Cs-corrected TEM. The phase detection limit improves by a factor of four. A further advantage is the possibility of fine-tuning the residual aberrations by a posteriori correction. Therefore, a combination of both methods, that is, Cs correction and off-axis electron holography, opens new perspectives for complete TEM analysis on an atomic scale. 相似文献
63.
Synthesis and catalytic properties of microemulsion-derived cerium oxide nanoparticles 总被引:2,自引:0,他引:2
Emanuel Kockrick Christian Schrage Anett Grigas Dorin Geiger Stefan Kaskel 《Journal of solid state chemistry》2008,181(7):1614-1620
The synthesis of cerium dioxide nanoparticles using an inverse microemulsion technique and precipitation method was investigated. Cerium hydroxide nanoparticles were synthesized by adding diluted ammonia to n-heptane–surfactant–cerium nitrate system. The micelle and particle size in the range of 5–12 nm were controlled by varying the molar water to surfactant ratio and analyzed by dynamic light scattering (DLS), small angle X-ray scattering (SAXS) and high-resolution transmission electron microscopy (HRTEM). Cerium hydroxide nanoparticles were isolated and subsequently treated at 100–600 °C to obtain nanoscale ceria. Crystallite sizes of cerium dioxide in the range of 6–16 nm were estimated by Scherrer analysis by X-ray diffraction (XRD) and HRTEM. The catalytic activity of particles annealed at 400 and 600 °C in soot combustion reactions was characterized by temperature-programmed oxidation (TPO) indicating a size-dependant activity. Crystallite sizes and catalytic stability of elevated ceria systems were tested in second combustion cycles. 相似文献
64.
65.
Laws DR Chong D Nash K Rheingold AL Geiger WE 《Journal of the American Chemical Society》2008,130(30):9859-9870
The anodic one-electron oxidation of three members of the half-sandwich family of piano-stool compounds MnCp (gamma)(CO) 3, where Cp (gamma) is a generic cyclopentadienyl ligand, has been studied in a CH 2Cl 2/[NBu 4][TFAB] electrolyte (TFAB = [B(C6F5) 4] (-)). The long-sought 17 e (-) radical cation of the parent complex MnCp(CO) 3 (cymantrene, 1, E 1/2 = 0.92 V vs ferrocene) has been shown to be persistent in solutions that use weakly coordinating anions in place of more nucleophilic traditional electrolyte anions. Spectroscopically characterized for the first time, 1 (+) was shown to absorb in the visible (530 nm), near-IR (2066 nm), and IR (2118, 1934 cm (-1)) regions. It was ESR-active at low temperatures (g parallel = 2.213, g perpendicular = 2.079, A parallel (Mn) = 79.2 G, A perpendicular (Mn) = 50 G) and NMR active at room temperature (delta = 22.4 vs TMS). The radical cations of the Cp-functionalized analogues, Mn(eta (5)-C5H 4NH2)(CO) 3, 2, E 1/2 = 0.62 V, and MnCp*(CO) 3 (Cp*= eta (5)-C 5Me 5, 3), E 1/2 = 0.64 V, were generated electrochemically as well by the chemical oxidant [ReCp(CO) 3] (+). The structures of 2 (+) and 3 (+) were determined by X-ray crystallographic studies of their TFAB salts. Compared to the structures of the corresponding neutral compounds, the cations showed elongated Mn-C(O) bonds and shortened C-O bonds, displaying the effect of diminished metal-to-CO backbonding. The bond-length changes in the Mn(CO) 3 moiety were much larger in 3 (+) (avg changes, Mn-C(O) = + 0.142 A, C-O = -0.063 A) than in 2 (+) (avg changes, Mn-C(O) = + 0.006 A, C-O = -0.003 A). Although there were only minor changes in the metal-to-center ring distances upon oxidation of either 2 or 3, there was decidedly less bending of the C(N) atom out of the cyclopentadienyl plane in 2 (+) compared to 2. The optical, vibrational, and magnetic resonance spectra of radicals 2 (+) and 3 (+) were also observed. The spectral data argue for the SOMOs of the 17-electron species being largely located on the Mn(CO) 3 moiety, having 40-50% Mn d-orbital character, with the ground states of the radicals, most likely (2)A', lying close in energy (within about 6000 cm (-1)) to excited states that are responsible for their rapid electronic relaxations. The cymantrenyl moiety is proposed as an anodic redox tag (or label) having physical and chemical properties that are significantly different from those of its ferrocenyl analogue. 相似文献
66.
Dynamic Nuclear Polarization Provides New Insights into Chromophore Structure in Phytochrome Photoreceptors
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Daniel Stöppler Dr. Chen Song Dr. Barth‐Jan van Rossum Michel‐Andreas Geiger Christina Lang Prof. Dr. Maria‐Andrea Mroginski Dr. Anil Pandurang Jagtap Prof. Dr. Snorri Th. Sigurdsson Prof. Dr. Jörg Matysik Prof. Dr. Jon Hughes Prof. Dr. Hartmut Oschkinat 《Angewandte Chemie (International ed. in English)》2016,55(52):16017-16020
67.
68.
Krafft C Sobottka SB Geiger KD Schackert G Salzer R 《Analytical and bioanalytical chemistry》2007,387(5):1669-1677
Infrared (IR) spectroscopy provides a sensitive molecular fingerprint for tissue without external markers. Supervised classification models can be trained to identify the tissue type based on the spectroscopic fingerprint. Infrared imaging spectrometers equipped with multi-channel detectors combine the spectral and spatial information. Tissue areas of 4 x 4 mm(2) can be analyzed within a few minutes in the macroscopic imaging mode. An approach is described to apply this methodology to human astrocytic gliomas, which are graded according to their malignancy from one to four. Multiple IR images of three tissue sections from one patient with a malignant glioma are acquired and assigned to the six classes normal brain tissue, astrocytoma grade II, astrocytoma grade III, glioblastoma multiforme grade IV, hemorrhage, and other tissue by a linear discriminant analysis model which was trained by data from a single-channel detector. Before the model is applied here, the spectra are shown to be virtually identical. The first specimen contained approximately 95% malignant glioma regions, that means astrocytoma grade III or glioblastoma. The smaller percentage of 12-34% malignant glioma in the second specimen is consistent with its location at the tumor periphery. The detection of less than 0.2% malignant glioma in the third specimen points to a location outside the tumor. The results were correlated with the cellularity of the tissue which was obtained from the histopathologic gold standard. Potential applications of IR spectroscopic imaging as a rapid tool to complement established diagnostic methods are discussed. 相似文献
69.
Maturation of inductively coupled plasma-mass spectrometry (ICP-MS) in terms of size, reliability, and cost has had a significant impact on its consideration as a viable detector for gas chromatography. Its generally excellent sensitivity for those elements it can measure has been a contributing factor. A method for sulfur speciation in various hydrocarbon products is investigated, as well as sulfur and metal hydride contaminants in high purity hydrocarbon feed stocks. Detection limits for sulfur species in hydrocarbon liquids and gases are approximately 5 and 10 ppb, respectively, as sulfur. Lower detection limits on the order of 100 parts per trillion are achieved for arsine. The use of collision cell technology (CCT) is exploited to remove interferences. CCT has been described elsewhere (1) using helium or helium-hydrogen mixtures for suppression of (16)O(16)O(+) interference with (32)S. In this work, a novel approach is investigated which uses oxygen to remove this interference by shifting it in a comprehensive fashion. The advantage of operating the system at full power with a tandem gas and liquid interface is also discussed. 相似文献
70.
We have synthesized a new class of flexible zwitterions 6a-e, in which a carboxylate is linked via an alkyl chain with variable length (one to five methylene groups) to a guanidiniocarbonylpyrrole cation. The self-association properties of these zwitterions were determined by NMR dilution studies in DMSO and by ESI-MS experiments. The stability and hence also the size of the aggregates formed via self-assembly is critically dependent on the length and therefore flexibility of the spacer. Whereas the smallest zwitterion 6a forms large aggregates already at low concentrations, the more flexible zwitterions only form small oligomers (6b) or dimers (6c-e) at much larger concentrations. The differences between the five zwitterions can be explained based on the different extent of intramolecular ion pairing within the monomers. Any intramolecular ion pairing, which becomes possible with increasing linker length, stabilizes the monomer and therefore destabilizes any oligomer. 相似文献