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111.
112.
Saalfrank RW Deutscher C Sperner S Nakajima T Ako AM Uller E Hampel F Heinemann FW 《Inorganic chemistry》2004,43(14):4372-4382
Reaction of various N-substituted diethanolamines H(2)L(3) (4) with calcium hydride and iron(III) chloride leads to the self-assembly of six-membered ferric wheels [Fe(6)X(6)(L(3))(6)] (5). Principally, all the iron coronands are isostructural; however, they differ fundamentally with respect to their crystal packing. Exemplarily, this is discussed for selected members of the space groups R, P, P2(1)/c, P2(1)/n, C2/c, and P. Depending on the nature of their sidearms, the ferric wheels create various substructures. For instance, the ferric wheels 5a-i of space group R or P are piled in parallel in cylindrical columns, which are surrounded by six parallel columns alternately dislocated by (1)/(3)c and (2)/(3)c against the central one. Pronounced van der Waals interactions give rise to compartmentation and incarceration of guest molecules as seen for 5e,g. However, in 5h strong pi-pi interactions create a three-dimensional scaffold. The most significant difference of the ferric wheels 5j-p of space groups P2(1)/c, P2(1)/n, and C2/c is that these ferric wheels are arranged in parallel in two orientations. They differ mainly only by the included angle of the two groups of parallel wheels. In the case of 5l, molecular chains are formed in the crystal due to pi-pi interactions. The ferric wheels 5q-y of space group P are packed in the crystal most simply, with all the ferric wheels piled in parallel. 相似文献
113.
Both, experimental investigation of protein adsorption processes and mathematical models describing such processes indicate, that the pH in the absorbent particle might be the key factor for an improved understanding of these chromatographic processes. Thus, a technique aiming at the spatially resolved pH measurement in macroscopic large absorbent particles is presented. The first application of this method, being based on confocal laser scanning microscopy (CLSM), revealed an apparent dependence of the pH calibration curve on the scanning depth. By a model-based approach, factors distorting the measurement signal are identified: The wavelength-dependent light scattering and the re-absorption of emitted light. The resulting consequences for further development and application of CLSM based techniques to measure pH in macroscopic large absorbent particles are illustrated and discussed. 相似文献
114.
Sellmann D Hautsch B Rösler A Heinemann FW 《Angewandte Chemie (International ed. in English)》2001,40(8):1505-1507
115.
We consider families of quadratic polynomials which admit parameterisations in a neighbourhood of the boundary of the Mandelbrot
set. We show how to find parameters such that the associated Julia sets are of Hausdorff dimension 2.
Received October 11, 1999 / Published online April 12, 2001 相似文献
116.
Christophe Werlé Chih-Juo Madeline Yin Frank W. Heinemann Christina Hauser Karsten Meyer 《Tetrahedron letters》2017,58(28):2715-2719
The efficient multi-step, large-scale synthesis, spectroscopic characterization and solid-state molecular structure of a new type of three-fold functionalized, sterically demanding triazine is reported. The aromatic heterocycle 6,6′,6′'-((1,3,5-triazine-2,4,6-triyl)tris(methylene))tris(2,4-di-tert-butylphenol) possesses three 2,4-di-tert-butylphenol synthons bound to the 1,3,5-triazine ring via synthetically challenging methylene linkages in the 2,4,6 positions. The key to success was found in the generation of a highly reactive imidate hydrochloride salt, namely ethyl 2-(3,5-di-tert-butyl-2-methoxyphenyl)acetimidate hydrochloride, that readily undergoes cyclotrimerization. The reported preparation opens new perspectives in the design and synthesis of novel triazine molecules bearing flexible and sterically demanding functionalized groups for various applications. 相似文献
117.
Timothy Hamerly Joshua Heinemann Monika Tokmina-Lukaszewska Elizabeth R. Lusczek Kristine E. Mulier Greg J. Beilman Brian Bothner 《Analytica chimica acta》2014
The potential for using serum albumin (SA) as a broadly applicable molecular sensor was explored in an effort to develop a method for rapid analysis of complex metabolite samples. SA is a protein present at high concentration in blood, which transports a diverse set of compounds including fatty acids, hormones, and drugs. The effectiveness of the bovine ortholog (BSA) as a molecular sensor was tested by analyzing the pool of small molecules bound to the protein after a brief incubation with complex fluids of biological origin. As an initial test, three varietals of red wine were readily distinguished. Further analysis using four varietals of white wine also showed clear separation. In a second analysis using urine, animals in hemorrhagic shock were separated from a group of comparably treated controls. A time course analysis showed that recovery from injury could also be followed using the assay. This finding is significant as there currently is no method or biomarker for predicting the onset of shock. Comparison of samples was based on liquid chromatography mass spectrometry (LCMS) analysis of compounds selectively bound by BSA. Analysis of the samples after protein selection revealed a significant reduction in complexity and clear separation of groups by Principle Component Analysis (PCA). These results show the potential for using cargo-carrying proteins as molecular sensors for screening complex samples without the need for prior knowledge of sample composition or concentration and may streamline elucidation of biomarkers. 相似文献
118.
Synthesis and Characterization of a Uranium(II) Monoarene Complex Supported by δ Backbonding
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Dr. Henry S. La Pierre Dr. Andreas Scheurer Dr. Frank W. Heinemann Priv.‐Doz. Dr. Wolfgang Hieringer Prof. Dr. Karsten Meyer 《Angewandte Chemie (International ed. in English)》2014,53(28):7158-7162
The low‐temperature (35 °C) reduction of the trivalent uranium monoarene complex [{(Ad,MeArO)3mes}U] ( 1 ), with potassium spheres in the presence of a slight excess of 2.2.2‐cryptand, affords the quantitative conversion of 1 into the uranium(II) monoarene complex [K(2.2.2‐crypt)][((Ad,MeArO)3mes)U] ( 1‐K ). The molecular and electronic structure of 1‐K was established experimentally by single‐crystal X‐ray diffraction, variable‐temperature 1H NMR and X‐band EPR spectroscopy, solution‐state and solid‐state magnetism studies, and optical absorption spectroscopy. The electronic structure of the complex was further investigated by DFT calculations. The complete body of evidence confirms that 1‐K is a uranium(II) monoarene complex with a 5f 4 electronic configuration supported by δ backbonding and that the nearly reversible, room‐temperature reduction observed for 1 at ?2.495 V vs. Fc/Fc+ is principally metal‐centered. 相似文献
119.
High Resolution Scanning Tunneling Microscopy of a 1D Coordination Polymer with Imidazole‐Based N,N,O Ligands on HOPG
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Dr. Nina V. Fischer Utpal Mitra Karl‐Georg Warnick Dr. Viacheslav Dremov Dr. Michael Stocker Thorsten Wölfle Dr. Wolfgang Hieringer Dr. Frank W. Heinemann Prof. Dr. Nicolai Burzlaff Prof. Dr. Andreas Görling Prof. Dr. Paul Müller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(37):11863-11869
Novel κ3‐N,N,O ligands tend to form 1D coordination polymer strands. Deposition of 1D structures on highly oriented pyrolytic graphite (HOPG) was achieved from diluted solutions and polymer strands have been studied on HOPG by AFM/STM. Single strands were mapped by STM and their electronic properties were subsequently characterized by current imaging tunneling spectroscopy (CITS). Periodic density functional calculations simulating a polymer strand deposited on a HOPG surface are in agreement with the zig‐zag structure indicated by experimental findings. Both the observed periodicity and the Zn–Zn distances can be reproduced in the simulations. Van der Waals interactions were found to play a major role for the geometry of the isolated polymer strand, for the adsorption geometry on HOPG, as well as for the adsorption energy. 相似文献
120.
Katharina Monczak Katrin Peuntinger Dieter Sorsche Dr. Frank W. Heinemann Prof. Dr. Dirk M. Guldi Prof. Dr. Sven Rau 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(47):15426-15433
The synthesis of a trisheteroleptic ruthenium complex [Ru(tb)(dppz)(tmbiH2)][PF6]2 (tb=4,4′‐di‐tert‐butyl‐2,2′‐bipyridine, dppz=dipyrido[3,2‐a:2′,3′‐c]phenazin, tmbiH2=5,6,5′,6′‐tetramethyl‐2,2′‐bibenzimidazole) is described. In addition, the structural characterisation by means of 1D, 2D 1H NMR spectroscopy, and mass spectrometry, along with determination of the solid‐state structure of the important precursor Ru(tb)(dppz)Cl2, supports the proposed octahedral coordination geometry. The capability of tmbiH2 to form hydrogen bonds is corroborated by the solid‐state structure. The photochemical characteristics of this complex can be described as a combination of the “light switch” effects, which are either attributed to the dppz or to the tmbiH2 ligand. To illustrate the molecule’s double switchable features, steady‐state absorption and emission measurements were performed, which include the determination of the quantum yield and the pKa values of the acidic protons of the tmbiH2 ligand. Notably, the emission lifetimes are sensitive to the solvents used. This phenomenon is due to a proton‐coupled deactivation of the excited metal‐to‐ligand charge transfer (MLCT) state of the complex. 相似文献