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41.
Lena Scherthan Sebastian F. M. Schmidt Hendrik Auerbach Tim Hochdrffer Juliusz A. Wolny Wenli Bi Jiyong Zhao Michael Y. Hu Tom Toellner E. Ercan Alp Dennis E. Brown Christopher E. Anson Annie K. Powell Volker Schünemann 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(11):3482-3487
Time‐domain synchrotron Mössbauer spectroscopy (SMS) based on the Mössbauer effect of 161Dy has been used to investigate the magnetic properties of a DyIII‐based single‐molecule magnet (SMM). The magnetic hyperfine field of [Dy(Cy3PO)2(H2O)5]Br3?2 (Cy3PO)?2 H2O?2 EtOH is with B0=582.3(5) T significantly larger than that of the free‐ion DyIII with a 6H15/2 ground state. This difference is attributed to the influence of the coordinating ligands on the Fermi contact interaction between the s and 4f electrons of the DyIII ion. This study demonstrates that 161Dy SMS is an effective local probe of the influence of the coordinating ligands on the magnetic structure of Dy‐containing compounds. 相似文献
42.
Selda Kabatas Paola Agüi‐Gonzalez Kim‐Ann Saal Sebastian Jhne Felipe Opazo Silvio O. Rizzoli Nhu T. N. Phan 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(11):3476-3481
Boron has been employed in materials science as a marker for imaging specific structures by electron energy loss spectroscopy (EELS) or secondary ion mass spectrometry (SIMS). It has a strong potential in biological analyses as well; however, the specific coupling of a sufficient number of boron atoms to a biological structure has proven challenging. Herein, we synthesize tags containing closo‐1,2‐dicarbadodecaborane, coupled to soluble peptides, which were integrated in specific proteins by click chemistry in mammalian cells and were also coupled to nanobodies for use in immunocytochemistry experiments. The tags were fully functional in biological samples, as demonstrated by nanoSIMS imaging of cell cultures. The boron signal revealed the protein of interest, while other SIMS channels were used for imaging different positive ions, such as the cellular metal ions. This allows, for the first time, the simultaneous imaging of such ions with a protein of interest and will enable new biological applications in the SIMS field. 相似文献
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Weise K Kapoor S Denter C Nikolaus J Opitz N Koch S Triola G Herrmann A Waldmann H Winter R 《Journal of the American Chemical Society》2011,133(4):880-887
The K-Ras4B GTPase is a major oncoprotein whose signaling activity depends on its correct localization to negatively charged subcellular membranes and nanoclustering in membrane microdomains. Selective localization and clustering are mediated by the polybasic farnesylated C-terminus of K-Ras4B, but the mechanisms and molecular determinants involved are largely unknown. In a combined chemical biological and biophysical approach we investigated the partitioning of semisynthetic fully functional lipidated K-Ras4B proteins into heterogeneous anionic model membranes and membranes composed of viral lipid extracts. Independent of GDP/GTP-loading, K-Ras4B is preferentially localized in liquid-disordered (l(d)) lipid domains and forms new protein-containing fluid domains that are recruiting multivalent acidic lipids by an effective, electrostatic lipid sorting mechanism. In addition, GDP-GTP exchange and, thereby, Ras activation results in a higher concentration of activated K-Ras4B in the nanoscale signaling platforms. Conversely, palmitoylated and farnesylated N-Ras proteins partition into the l(d) phase and concentrate at the l(d)/l(o) phase boundary of heterogeneous membranes. Next to the lipid anchor system, the results reveal an involvement of the G-domain in the membrane interaction process by determining minor but yet significant structural reorientations of the GDP/GTP-K-Ras4B proteins at lipid interfaces. A molecular mechanism for isoform-specific Ras signaling from separate membrane microdomains is postulated from the results of this study. 相似文献
45.
Tobias Schulz Dr. Sebastian Ahrens Dirk Meyer Christoph Allolio Anke Peritz Prof. Dr. Thomas Strassner 《化学:亚洲杂志》2011,6(3):863-867
Owing to numerous new applications, the interest in “task‐specific” ionic liquids increased significantly over the last decade. But, unfortunately, the imidazolium‐based ionic liquids (by far the most frequently used cations) have serious limitations when it comes to modifications of their properties. The new generation of ionic liquids, called tunable aryl–alkyl ionic liquids (TAAILs), replaces one of the two alkyl chains on the imidazolium ring with an aryl ring which allows a large degree of functionalization. Inductive, mesomeric, and steric effects as well as potentially also π π and π π+ interactions provide a wide range of possibilities to tune this new class of ILs. We investigated the influence of electron‐withdrawing and ‐donating substituents at the para‐position of the aryl ring (NO2, Cl, Br, EtO(CO), H, Me, OEt, OMe) by studying the changes in the melting points of the corresponding bromide and bis(trifluoromethanesulfonyl)imide, (N(Tf)2−), salts. In addition, we calculated (B3LYP/6‐311++G(d,p)) the different charge distributions of substituted 1‐aryl‐3‐propyl‐imidazolium cations to understand the experimentally observed effects. The results indicated that the presence of electron‐donating and ‐withdrawing groups leads to strong polarization effects in the cations. 相似文献
46.
This work describes a novel type of working electrode for use in voltammetry and polarography — the renewable silver liquid amalgam film–modified silver solid amalgam annular band electrode (AgLAF–AgSAE). The electrode is produced by mechanically refreshing the silver liquid amalgam film (AgLAF) before each measurement. The main constituents of the electrode are: a specially constructed silver solid amalgam annular band electrode (AgSAE), two silicon O-rings, silver liquid amalgam and a polypropylene electrode body. Contaminants from the analyzed solution are removed and the AgSAE surface is covered with a thick layer of fresh amalgam while pulling the AgSAE into the sensor body. During movement in the reverse direction AgLAF is formed and homogenized. The time needed to refresh the film is less than 1 s. The electrode is characterized by excellent surface repeatability (~ 1%) and long-term stability (over ten thousand measurement cycles). 相似文献
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Lukas Fritz Dr. Sebastian Wienhold Sabrina Hackl Prof. Dr. Thorsten Bach 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(3):e202104064
A synthetic route to the pulvomycin class of natural products is presented, which culminated in the first synthesis of a pulvomycin, pulvomycin D. Key elements of the strategy include a pivotal aldol reaction which led to bond formation between the C24-C40 and the C8-C23 fragment. The remaining C1-C7 fragment was attached by a Yamaguchi esterification completing the assembly of the 40 carbon atoms within the main skeleton. Ring closure to the 22-membered lactone ring was achieved in the final stages of the synthesis by a Heck reaction. The completion of the synthesis required the removal of six silyl protecting groups in combination with olefin formation at C26-C27 by a Peterson elimination. 相似文献
50.
Kurt F. Hoffmann Dr. Anja Wiesner Dr. Simon Steinhauer Prof. Dr. Sebastian Riedel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(57):e202201958
Preparation and characterization of the dimeric Lewis superacid [Al(OTeF5)3]2 and various solvent adducts is presented. The latter range from thermally stable adducts to highly reactive, weakly bound species. DFT calculations on the ligand affinity of these Lewis acids were performed in order to rank their remaining Lewis acidity. An experimental proof of the Lewis acidity is provided by the reaction of solvent-adducts of Al(OTeF5)3 with [PPh4][SbF6] and OPEt3, respectively. Furthermore, their reactivity towards chloride and pentafluoroorthotellurate salts as well as (CH3)3SiCl and (CH3)3SiF is shown. This includes the formation of the dianion [Al(OTeF5)5]2−. 相似文献