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101.
Suihan Feng Dr. Vibor Laketa Frank Stein Dr. Anna Rutkowska Dr. Aidan MacNamara Dr. Sofia Depner Prof. Ursula Klingmüller Dr. Julio Saez‐Rodriguez Priv.‐Doz. Dr. Carsten Schultz 《Angewandte Chemie (International ed. in English)》2014,53(26):6720-6723
Chemical dimerizers are powerful tools for non‐invasive manipulation of enzyme activities in intact cells. Here we introduce the first rapidly reversible small‐molecule‐based dimerization system and demonstrate a sufficiently fast switch‐off to determine kinetics of lipid metabolizing enzymes in living cells. We applied this new method to induce and stop phosphatidylinositol 3‐kinase (PI3K) activity, allowing us to quantitatively measure the turnover of phosphatidylinositol 3,4,5‐trisphosphate (PIP3) and its downstream effectors by confocal fluorescence microscopy as well as standard biochemical methods. 相似文献
102.
Christian Schumacher Dr. José G. Hernández Prof. Dr. Carsten Bolm 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(38):16499-16502
The formation and regeneration of active CuI species is a fundamental mechanistic step in copper-catalyzed atom transfer radical cyclizations (ATRC). Typically, the presence of the catalytically active CuI species in the reaction mixture is secured by using high CuI catalyst loadings or the addition of complementary reducing agents. In this study it is demonstrated how the piezoelectric properties of barium titanate (BaTiO3) can be harnessed by mechanical ball milling to induce electrical polarization in the strained piezomaterial. This strategy enables the conversion of mechanical energy into electrical energy, leading to the reduction of a CuII precatalyst into the active CuI species in copper-catalyzed mechanochemical solvent-free ATRC reactions. 相似文献
103.
Fabian Dankert H. Lars Deubner Matthias Müller Magnus R. Buchner Florian Kraus Carsten von Hänisch 《无机化学与普通化学杂志》2020,646(18):1501-1507
The work describes unexpected stoichiometric C–F bond cleavage reactions of beryllium, magnesium, gallium, hafnium and thorium halides with α,α,α-trifluorotoluene. The reaction of BeBr2 / GaBr3 or MgBr2 / GaBr3 mixtures as well as neat GaI3 with α,α,α-trifluorotoluene in the presence of (OSi2Me4)2 ( I ) yields the carbenium ion containing compounds [Ph-C(O2Si2Me4)][GaX4] (X = Br: 1 , X = I/F: 2 ). Both compounds were successfully characterized and a defluorination type reaction under incorporation of a siloxy unit was observed. Compound 1 was also characterized by single-crystal X-ray diffraction analysis. The conversion of α,α,α-trifluorotoluene with BeI2, HfI4 or ThI4 turned out to be a halodefluorination-type reaction with formation of α,α,α-triiodotoluene ( 3 ). An adequate NMR spectroscopic and the X-ray crystallographic characterization of 3 were performed for the first time. 相似文献
104.
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106.
Chongqing Wang Christopher Lambert Maurice Hauser Adrian Deuschmann Dr. Carsten Zeilinger Prof. Dr. Klemens Rottner Prof. Dr. Theresia E. B. Stradal Prof. Dr. Marc Stadler Dr. Elizabeth J. Skellam Prof. Dr. Russell J. Cox 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(60):13578-13583
Mutasynthesis of pyrichalasin H from Magnaporthe grisea NI980 yielded a series of unprecedented 4′-substituted cytochalasin analogues in titres as high as the wild-type system (≈60 mg L−1). Halogenated, O-alkyl, O-allyl and O-propargyl examples were formed, as well as a 4′-azido analogue. 4′-O-Propargyl and 4′-azido analogues reacted smoothly in Huisgen cycloaddition reactions, whereas p-Br and p-I compounds reacted in Pd-catalysed cross-coupling reactions. A series of examples of biotin-linked, dye-linked and dimeric cytochalasins was rapidly created. In vitro and in vivo bioassays of these compounds showed that the 4′-halogenated and azido derivatives retained their cytotoxicity and antifungal activities; but a unique 4′-amino analogue was inactive. Attachment of larger substituents attenuated the bioactivities. In vivo actin-binding studies with adherent mammalian cells showed that actin remains the likely intracellular target. Dye-linked compounds revealed visualisation of intracellular actin structures even in the absence of phalloidin, thus constituting a potential new class of actin-visualisation tools with filament-barbed end-binding specificity. 相似文献
107.
Dr. Joydev Hatai Dr. Christoph Hirschhäuser Prof. Dr. Carsten Schmuck Dr. Jochen Niemeyer 《ChemistryOpen》2020,9(7):786-792
A coumarin based probe for the efficient detection of hydrogen sulfide in aqueous medium is reported. The investigated coumarine-based derivative forms spherical nanoparticles in aqueous media. In presence of Pd2+, a metallosupramolecular coordination polymer is formed, which is accompanied by quenching of the coumarin emission at 390 nm. Its Pd2+ complex could be used as a probe for chemoselective detection of monohydrogensulfide (HS−). Presence of HS− leads to a'turn-on' fluorescence signal, resulting from decomplexation of Pd2+ from the metallosupramolecular probe. The probe was successfully applied for qualitative and quantitative detection of HS− in different sources of water directly collected from sea, river, tap and laboratory drain water, as well as in growth media for aquatic species. 相似文献
108.
Karen J. Ardila‐Fierro Stipe Lukin Martin Etter Krunoslav Uarevi Ivan Halasz Carsten Bolm Jos G. Hernndez 《Angewandte Chemie (International ed. in English)》2020,59(32):13458-13462
Recent progress in the field of mechanochemistry has expanded the discovery of mechanically induced chemical transformations to several areas of science. However, a general fundamental understanding of how mechanochemical reactions by ball milling occur has remained unreached. For this, we have now implemented in situ monitoring of a mechanochemically induced molecular rearrangement by synchrotron X‐ray powder diffraction, Raman spectroscopy, and real‐time temperature sensing. The results of this study demonstrate that molecular rearrangements can be accomplished in the solid state by ball milling and how in situ monitoring techniques enable the visualization of changes occurring at the exact instant of a molecular migration. The mechanochemical benzil–benzilic acid rearrangement is the focal point of the study. 相似文献
109.
Carsten Kegler Helge B. Bode 《Angewandte Chemie (International ed. in English)》2020,59(32):13463-13467
The interaction in multisubunit non‐ribosomal peptide synthetases (NRPSs) is mediated by docking domains that ensure the correct subunit‐to‐subunit interaction. We introduced natural docking domains into the three‐module xefoampeptide synthetase (XfpS) to create two to three artificial NRPS XfpS subunits. The enzymatic performance of the split biosynthesis was measured by absolute quantification of the products by HPLC‐ESI‐MS. The connecting role of the docking domains was probed by deleting integral parts of them. The peptide production data was compared to soluble protein amounts of the NRPS using SDS‐PAGE. Reduced peptide synthesis was not a result of reduced soluble NRPS concentration but a consequence of the deletion of vital docking domain parts. Splitting the xefoampeptide biosynthesis polypeptide by introducing docking domains was feasible and resulted in higher amounts of product in one of the two tested split‐module cases compared to the full‐length wild‐type enzyme. 相似文献
110.
Dr. Ivan Fernandez-Corbaton Dominik Beutel Prof. Dr. Carsten Rockstuhl Ansgar Pausch Prof. Dr. Wim Klopper 《Chemphyschem》2020,21(9):878-887
We outline a methodology for efficiently computing the electromagnetic response of molecular ensembles. The methodology is based on the link that we establish between quantum-chemical simulations and the transfer matrix (T-matrix) approach, a common tool in physics and engineering. We exemplify and analyze the accuracy of the methodology by using the time-dependent Hartree-Fock theory simulation data of a single chiral molecule to compute the T-matrix of a cross-like arrangement of four copies of the molecule, and then computing the circular dichroism of the cross. The results are in very good agreement with full quantum-mechanical calculations on the cross. Importantly, the choice of computing circular dichroism is arbitrary: Any kind of electromagnetic response of an object can be computed from its T-matrix. We also show, by means of another example, how the methodology can be used to predict experimental measurements on a molecular material of macroscopic dimensions. This is possible because, once the T-matrices of the individual components of an ensemble are known, the electromagnetic response of the ensemble can be efficiently computed. This holds for arbitrary arrangements of a large number of molecules, as well as for periodic or aperiodic molecular arrays. We identify areas of research for further improving the accuracy of the method, as well as new fundamental and technological research avenues based on the use of the T-matrices of molecules and molecular ensembles for quantifying their degrees of symmetry breaking. We provide T-matrix-based formulas for computing traditional chiro-optical properties like (oriented) circular dichroism, and also for quantifying electromagnetic duality and electromagnetic chirality. The formulas are valid for light-matter interactions of arbitrarily-high multipolar orders. 相似文献