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1.
Analyse von Protease‐Inhibitor‐Interaktionen unter Nutzung evolvierbarer tricyclischer Microviridine
2.
Annika Höhn Petra Hartmann Veronika Gebhart Johanna Sonntag Tilman Grune Tobias Jung 《Photochemistry and photobiology》2015,91(4):887-894
In this study, the athermal effects of water‐filtered infrared A (wIRA)‐irradiation (780–1400 nm) on human dermal fibroblasts were investigated. For this purpose, cells were exposed to wIRA‐irradiation (178 mW cm?2 for 1 h), while a sophisticated experimental setup prevented warming of the samples exceeding 0.1°C. The investigated parameters were the formation of reactive oxygen species (ROS), mitochondrial membrane potential and superoxide release, protein oxidation, proliferation rate, as well as intracellular Ca2+‐release in single cells, most of them quantified via fluorescence microscopy and fluorimetric techniques. The existence of actual athermal wIRA‐effects is still intensively discussed, since their detection requires a careful experimental setup and both efficient and powerful temperature regulation of the exposed samples. Here, we can definitively show that some of the supposed athermal wIRA‐effects may be rather artifacts, since wIRA did not reveal any impact on the above mentioned parameters—as long as the temperature of the exposed cells was carefully maintained. Though, we were able to identify an athermal DNA‐protective wIRA‐effect, since the induced DNA damage (quantified via 8‐Oxo‐G‐formation) was significantly decreased after a subsequent UVB‐exposure. These results suggest that many of the supposed athermal wIRA‐effects can be induced by pure warming of the samples, independent from any wIRA‐irradiation. 相似文献
3.
Dr. Tobias W. Giessen Florian Altegoer Annika J. Nebel Roman M. Steinbach Dr. Gert Bange Prof. Dr. Mohamed A. Marahiel 《Angewandte Chemie (International ed. in English)》2015,54(8):2492-2496
The incorporation of non‐proteinogenic amino acids represents a major challenge for the creation of functionalized proteins. The ribosomal pathway is limited to the 20–22 proteinogenic amino acids while nonribosomal peptide synthetases (NRPSs) are able to select from hundreds of different monomers. Introduced herein is a fusion‐protein‐based design for synthetic tRNA‐aminoacylation catalysts based on combining NRPS adenylation domains and a small eukaryotic tRNA‐binding domain (Arc1p‐C). Using rational design, guided by structural insights and molecular modeling, the adenylation domain PheA was fused with Arc1p‐C using flexible linkers and achieved tRNA‐aminoacylation with both proteinogenic and non‐proteinogenic amino acids. The resulting aminoacyl‐tRNAs were functionally validated and the catalysts showed broad substrate specificity towards the acceptor tRNA. Our strategy shows how functional tRNA‐aminoacylation catalysts can be created for bridging the ribosomal and nonribosomal worlds. This opens up new avenues for the aminoacylation of tRNAs with functional non‐proteinogenic amino acids. 相似文献
4.
Johannes C. B. Dietschreit Annika Wagner T. Anh Le Philipp Klein Prof. Dr. Hermann Schindelin Prof. Dr. Till Opatz Prof. Dr. Bernd Engels Prof. Dr. Ute A. Hellmich Prof. Dr. Christian Ochsenfeld 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(31):12769-12773
The absence of fluorine from most biomolecules renders it an excellent probe for NMR spectroscopy to monitor inhibitor–protein interactions. However, predicting the binding mode of a fluorinated ligand from a chemical shift (or vice versa) has been challenging due to the high electron density of the fluorine atom. Nonetheless, reliable 19F chemical-shift predictions to deduce ligand-binding modes hold great potential for in silico drug design. Herein, we present a systematic QM/MM study to predict the 19F NMR chemical shifts of a covalently bound fluorinated inhibitor to the essential oxidoreductase tryparedoxin (Tpx) from African trypanosomes, the causative agent of African sleeping sickness. We include many protein–inhibitor conformations as well as monomeric and dimeric inhibitor–protein complexes, thus rendering it the largest computational study on chemical shifts of 19F nuclei in a biological context to date. Our predicted shifts agree well with those obtained experimentally and pave the way for future work in this area. 相似文献
5.
Toluene has been identified as a novel carrier of xanthates. Their corresponding fragmentative precursors proved to behave efficiently in radical group transfer reactions. As examples, unprecedented S-tri/di-chloromethyl xanthates could be prepared, isolated and further used in radical additions to olefins. Their precursors (de-aromatized toluene upon which is grafted, at one end, a tri/di-chloromethyl-group and, at the other end, a dithiocarbonyl group) can also be used directly in the transfer of both groups to olefins. The re-aromatizing loss of toluene by radical initiated fragmentation of the precursors brings thus new opportunities to the chemistry of xanthates, exemplified here in the intermolecular additions to olefins of new S-tri/di-chloromethyl xanthates. 相似文献
6.
N‐Heterocyclic Silylenes in Boron Chemistry: Facile Formation of Silylboranes and Silaborinines 下载免费PDF全文
Annika Gackstatter Prof. Dr. Holger Braunschweig Dr. Thomas Kupfer Christian Voigt Dr. Nicole Arnold 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(46):16415-16419
Reaction of a N‐heterocyclic silylene (NHSi) with PhBX2 (X=Cl, Br) readily afforded six‐membered silaborinines through an insertion/ring expansion sequence. Increasing the sterics of the borane from phenyl to duryl enabled the selective generation and isolation of the highly colored silylborane intermediates. Theoretical studies on the mechanism and energetics of the silaborinine formation were fully consistent with the experimental observations. 相似文献
7.
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9.
Dr. Mohd Nazish Dr. Mujahuddin M. Siddiqui Dr. Samir Kumar Sarkar Dr. Annika Münch Christina M. Legendre Dr. Regine Herbst-Irmer Prof. Dietmar Stalke Prof. Dr. Herbert W. Roesky 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(5):1744-1752
This work describes the synthesis and coordination behavior of a new mixed-donor ligand PhC(NtBu)2SiC6H4PPh2 ( 1 ) containing both silylene and phosphine donor sites. Ligand 1 was synthesized from a reaction of ortho-lithiated diphenylphosphinobenzene (LiC6H4PPh2) with chlorosilylene (PhC(NtBu)2SiCl). Treatment of 1 with Se and GeCl2 resulted in SiIV compounds 2 and 3 by selective oxidation of the silylene donor. This strong σ-donor ligand induces dissociation of CuCl and PhBCl2 leading to formation of ionic complexes 4 and 5 respectively. The reaction of 1 with ZnCl2 and AlCl3 resulted in the formation of chelate complexes 5 and 7 , respectively, while treatment with EtAlCl2 and GaCl3 forms monodentate complexes 8 and 9 . X-ray analysis of 4 showed that the copper is in the spiro center of the two five-membered rings. Moreover, the copper(I)chloride has not been oxidized but dissociates to Cu+ and [CuCl2]−. All the compounds are well characterized by mass spectrometry, elemental analysis, NMR spectroscopy, and single-crystal X-ray diffraction studies. 相似文献
10.
Lars Radke Christoph Giese Annika Lubitz Stephan Hinderlich Grit Sandig Michael Hummel Marcus Frohme 《Mikrochimica acta》2014,181(13-14):1733-1742
Quantitative real-time PCR (qPCR) is commonly used for gene expression analyses with defined documentation guidelines to compare published results. To minimize the impact of variances from qPCR performance, sample handling and processing reference genes are used. Their selection process cannot be completely aligned due to variations in experimental conditions. Furthermore, the named sources of error are also present when determining the stability of the reference genes themselves. Even software applications that are used to identify the best reference genes rarely coincide on their rankings and can be misleading under certain conditions. In previous experiments, peripheral blood mononuclear cells (PBMC) were analyzed to identify the most stable reference gene(s). Twelve of the 13 investigated genes showed sample type specific differences in the expression. Direct mRNA measurement was performed in the form of a NanoString analysis, a multiplexed absolute quantification method. The external validation showed a high concordance of the reference gene expression levels. However, it identified the same sample type specific expression pattern for only some of the tested reference genes. By comparing various combinations of reference genes with both methods we are able to suggest a set of well-performing reference genes. Figure