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Jan-Niklas Dienemann Shu-Yu Chen Manuel Hitzenberger Montana L. Sievert Stephan M. Hacker Sean T. Prigge Martin Zacharias Michael Groll Stephan A. Sieber 《Angewandte Chemie (International ed. in English)》2023,62(31):e202304533
The development of novel anti-infectives requires unprecedented strategies targeting pathways which are solely present in pathogens but absent in humans. Following this principle, we developed inhibitors of lipoic acid ( LA ) salvage, a crucial pathway for the survival of LA auxotrophic bacteria and parasites but non-essential in human cells. An LA -based probe was selectively transferred onto substrate proteins via lipoate protein ligase (LPL) in intact cells, and their binding sites were determined by mass spectrometry. Probe labeling served as a proxy of LPL activity, enabling in situ screenings for cell-permeable LPL inhibitors. Profiling a focused compound library revealed two substrate analogs ( LAMe and C3 ) as inhibitors, which were further validated by binding studies and co-crystallography. Importantly, LAMe exhibited low toxicity in human cells and achieved killing of Plasmodium falciparum in erythrocytes with an EC50 value of 15 μM, making it the most effective LPL inhibitor reported to date. 相似文献
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Hyehwang Kim Dr. Zheng-wang Qu Prof. Dr. Stefan Grimme Nahil Al-Zuhaika Prof. Dr. Douglas W. Stephan 《Angewandte Chemie (International ed. in English)》2023,62(43):e202312587
The phosphino-phosphonium cations of the form [R3PPR′2]+ are labile and provide access to the constituent Lewis acidic and Lewis basic fragments. This permits frustrated Lewis pair-type addition reactions to alkynes, affording unprecedented phosphino-phosphination reactions and giving cations of the form [cis-R3PCHC(R′′)PR′2]+. This reactivity is further adapted to prepare several examples of a rare class of dissymmetric cis-olefin-linked bidentate phosphines. 相似文献
96.
Kinran Lau Felix Niemann Dr. Kaltum Abdiaziz Dr. Markus Heidelmann Yuke Yang Dr. Yujin Tong Dr. Michael Fechtelkord Prof. Torsten C. Schmidt Dr. Alexander Schnegg Prof. R. Kramer Campen Dr. Baoxiang Peng Prof. Martin Muhler Dr. Sven Reichenberger Prof. Stephan Barcikowski 《Angewandte Chemie (International ed. in English)》2023,62(12):e202213968
Both oxygen vacancies and surface hydroxyls play a crucial role in catalysis. Yet, their relationship is not often explored. Herein, we prepare two series of TiO2 (rutile and P25) with increasing oxygen deficiency and Ti3+ concentration by pulsed laser defect engineering in liquid (PUDEL), and selectively quantify the acidic and basic surface OH by fluoride substitution. As indicated by EPR spectroscopy, the laser-generated Ti3+ exist near the surface of rutile, but appear to be deeper in the bulk for P25. Fluoride substitution shows that extra acidic bridging OH are selectively created on rutile, while the surface OH density remains constant for P25. These observations suggest near-surface Ti3+ are highly related to surface bridging OH, presumably the former increasing the electron density of the bridging oxygen to form more of the latter. We anticipate that fluoride substitution will enable better characterization of surface OH and its correlation with defects in metal oxides. 相似文献
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Dr. Carolin Müller Alexander Schwab Dr. Nicholas M. Randell Dr. Stephan Kupfer Prof. Benjamin Dietzek-Ivanšić Dr. Murielle Chavarot-Kerlidou 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(18):e202103882
The design of photoactive systems capable of storing and relaying multiple electrons is highly demanded in the field of artificial photosynthesis, where transformations of interest rely on multielectronic redox processes. The photophysical properties of the ruthenium photosensitizer [(bpy)2Ru( oxim-dppqp )]2+ ( Ru ), storing two electrons coupled to two protons on the π-extended oxim-dppqp ligand under light-driven conditions, are investigated by means of excitation wavelength-dependent resonance Raman and transient absorption spectroscopies, in combination with time-dependent density functional theory; the results are discussed in comparison to the parent [(bpy)2Ru(dppz)]2+ and [(bpy)2Ru( oxo-dppqp )]2+ complexes. In addition, this study provides in-depth insights on the impact of protonation or of accumulation of multiple reducing equivalents on the reactive excited states. 相似文献
98.
Christopher J. Major Dr. Zheng-Wang Qu Prof. Dr. Stefan Grimme Prof. Dr. Douglas W. Stephan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(27):e202200698
The known boranes (R(Me3Si)N)2BF (R=Me3Si 1 , tBu 2 , C6F5 3 , o-tol 4 , Mes 5 , Dipp 6 ) and borinium salts (R(Me3Si)N)2B][B(C6F5)4] (R=Me3Si 7 , tBu 8 ) are prepared and fully characterized. Compound 7 is shown to react with phosphines to generate [R3PSiMe3]+ and [R3PH]+ (R=Me, tBu). Efforts to generate related borinium cations via fluoride abstraction from (R(Me3Si)N)2BF (R=C6F5 3 , o-tol 4 , Mes 5 ) gave complex mixtures suggesting multiple reaction pathways. However for R=Dipp 6 , the species [(μ-F)(SiMe2N(Dipp))2BMe][B(C6F5)4] was isolated as the major product, indicating methyl abstraction from silicon and F/Me exchange on boron. These observations together with state-of-the-art DFT mechanistic studies reveal that the trimethylsilyl-substituents do not behave as ancillary subsitutents but rather act as sources of proton, SiMe3 and methyl groups. 相似文献
99.
Dr. Anna R. Ziefuss Michael Willeke Matthias Miertz Dr. Alexander Heinemann Dr. Christoph Rehbock Prof. Dr. Stephan Barcikowski 《Chemphyschem》2022,23(10):e202200033
Noble metal alloy nanoclusters (NCs) are interesting systems as the properties of two or more elements can be combined in one particle, leading to interesting fluorescence phenomena. However, previous studies have been exclusively performed on ligand-capped NCs from wet chemical synthesis. This makes it difficult to differentiate to which extent the fluorescence is affected by ligand-induced effects or the elemental composition of the metal core. In this work, we used laser fragmentation in liquids (LFL) to fabricate colloidal gold-rich bi-metallic AuPt NCs in the absence of organic ligands and demonstrate the suitability of this technique to produce molar fraction series of 1nm alloy NC. We found that photoluminescence of ligand-free NCs is not a phenomenon limited to Au. However, even minute amounts of Pt atoms in the AuPt NCs lead to quenching and red-shift of the fluorescence, which may be attributed to the altered surface charge density. 相似文献
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