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Felix Nußbaumer Raphael Plangger Manuel Roeck Christoph Kreutz 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(39):17210-17217
We present the access to [5-19F, 5-13C]-uridine and -cytidine phosphoramidites for the production of site-specifically modified RNAs up to 65 nucleotides (nts). The amidites were used to introduce [5-19F, 5-13C]-pyrimidine labels into five RNAs—the 30 nt human immunodeficiency virus trans activation response (HIV TAR) 2 RNA, the 61 nt human hepatitis B virus ϵ (hHBV ϵ) RNA, the 49 nt SAM VI riboswitch aptamer domain from B. angulatum, the 29 nt apical stem loop of the pre-microRNA (miRNA) 21 and the 59 nt full length pre-miRNA 21. The main stimulus to introduce the aromatic 19F–13C-spin topology into RNA comes from a work of Boeszoermenyi et al., in which the dipole-dipole interaction and the chemical shift anisotropy relaxation mechanisms cancel each other leading to advantageous TROSY properties shown for aromatic protein sidechains. This aromatic 13C–19F labeling scheme is now transferred to RNA. We provide a protocol for the resonance assignment by solid phase synthesis based on diluted [5-19F, 5-13C]/[5-19F] pyrimidine labeling. For the 61 nt hHBV ϵ we find a beneficial 19F–13C TROSY enhancement, which should be even more pronounced in larger RNAs and will facilitate the NMR studies of larger RNAs. The [19F, 13C]-labeling of the SAM VI aptamer domain and the pre-miRNA 21 further opens the possibility to use the biorthogonal stable isotope reporter nuclei in in vivo NMR to observe ligand binding and microRNA processing in a biological relevant setting. 相似文献
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Tobramycin and Nebramine as Pseudo‐oligosaccharide Scaffolds for the Development of Antimicrobial Cationic Amphiphiles 下载免费PDF全文
Yifat Berkov‐Zrihen Ido M. Herzog Raphael I. Benhamou Dr. Mark Feldman Kfir B. Steinbuch Pazit Shaul Dr. Shachar Lerer Dr. Avigdor Eldar Dr. Micha Fridman 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(11):4340-4349
Antimicrobial cationic amphiphiles derived from aminoglycoside pseudo‐oligosaccharide antibiotics interfere with the structure and function of bacterial membranes and offer a promising direction for the development of novel antibiotics. Herein, we report the design and synthesis of cationic amphiphiles derived from the pseudo‐trisaccharide aminoglycoside tobramycin and its pseudo‐disaccharide segment nebramine. Antimicrobial activity, membrane selectivity, mode of action, and structure–activity relationships were studied. Several cationic amphiphiles showed marked antimicrobial activity, and one amphiphilic nebramine derivative proved effective against all of the tested strains of bacteria; furthermore, against several of the tested strains, this compound was well over an order of magnitude more potent than the parent antibiotic tobramycin, the membrane‐targeting antimicrobial peptide mixture gramicidin D, and the cationic lipopeptide polymyxin B, which are in clinical use. 相似文献
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Raphael I. Benhamou Kfir B. Steinbuch Dr. Micha Fridman 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(32):11148-11151
Herein we report that an imidazole‐decorated cationic amphiphile derived from the pseudo‐disaccharide nebramine has potent antifungal activity against strains of Candida glabrata pathogens. In combination with the natural bis‐benzylisoquinoline alkaloid tetrandrine the reported antifungal cationic amphiphile demonstrated synergistic antifungal activity against Candida albicans pathogens. This unique membrane disruptor caused no detectible mammalian red blood cell hemolysis at concentrations up to more than two orders of magnitude greater than its minimal inhibitory concentrations against the tested C. glabrata strains. We provide evidence that potency against C. glabrata may be associated with differences between the drug efflux pumps of C. albicans and C. glabrata. Imidazole decorated‐cationic amphiphiles show promise for the development of less toxic membrane‐disrupting antifungal drugs and drug combinations. 相似文献
6.
Luís Antônio Dantas Silva Fernanda Vieira Teixeira Raphael Caixeta Serpa Najla Locatelli Esteves Rayane Ramos dos Santos Eliana Martins Lima Marcílio Sérgio Soares da Cunha-Filho Adriano Antunes de Souza Araújo Stephânia Fleury Taveira Ricardo Neves Marreto 《Journal of Thermal Analysis and Calorimetry》2016,123(3):2337-2344
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Dr. Maximilian Muhr Hao Liang Dr. Lars Allmendinger Raphael Bühler Fabrizio E. Napoli Dr. Dardan Ukaj Dr. Mirza Cokoja Dr. Christian Jandl Dr. Samia Kahlal Prof. Dr. Jean-Yves Saillard Dr. Christian Gemel Prof. Dr. Roland A. Fischer 《Angewandte Chemie (International ed. in English)》2023,62(36):e202308790
The bimetallic, decanuclear Ni3Ga7-cluster of the formula [Ni3(GaTMP)3(μ2-GaTMP)3(μ3-GaTMP)] ( 1 , TMP=2,2,6,6-tetramethylpiperidinyl) reacts reversibly with dihydrogen under the formation of a series of (poly-)hydride clusters 2 . Low-temperature 2D NMR experiments at −80 °C show that 2 consist of a mixture of a di- ( 2Di ), tetra- ( 2Tetra ) and hexahydride species ( 2Hexa ). The structures of 2Di and 2Tetra are assessed by a combination of 2D NMR spectroscopy and DFT calculations. The cooperation of both metals is essential for the high hydrogen uptake of the cluster. Polyhydrides 2 are catalytically active in the semihydrogenation of 4-octyne to 4-octene with good selectivity. The example is the first of its kind and conceptually relates properties of molecular, atom-precise transition metal/main group metal clusters to the respective solid-state phase in catalysis. 相似文献
9.
Immanuel Plangger Dr. Tobias Pinkert Dr. Klaus Wurst Prof. Dr. Thomas Magauer 《Angewandte Chemie (International ed. in English)》2023,62(32):e202307719
We present a concise asymmetric total synthesis (5–8 steps) of nine sesquiterpenoid alkaloids featuring four different tetra-/pentacyclic scaffolds. To this end, a novel, bioinspired indole N-terminated cationic tricyclization has been developed, enabling the divergent synthesis of greenwayodendrines and polysin. Subtle variation of the C2-substituted indole cyclization precursor allowed switching between indole N- and C-termination. For the latter, a subsequent Witkop oxidation enabled conversion of the cyclopentene-fused indole into the eight-membered benzolactam to directly furnish the family of greenwaylactams. In addition, a diastereomeric C-termination product has been elaborated to provide access to polyveoline. 相似文献
10.
Jarno Riefer Ludwig Zapf Dr. Raphael Wirthensohn Dr. Philipp T. Hennig Dr. Tatjana Ribbeck Dr. Jan A. P. Sprenger Dr. Nikolai V. Ignat'ev Prof. Dr. Maik Finze 《European journal of organic chemistry》2023,26(17):e202300031
Cyanoborane adducts of the Lewis acids B(CN)3, BF(CN)2, and BH(CN)2 with pyridine and 4-cyanopyridine have been obtained in high yields. The syntheses were accomplished by oxidation of the readily available potassium salts of the cyano(hydrido)borate anions [BH(CN)3]− ( MHB ), [BFH(CN)2]− ( FHB ), and [BH2(CN)2]− ( DHB ) with bromine in the presence of the respective pyridine derivative C5H5N or 4-CN-C5H4N as starting material. All six cyanoborane adducts have been characterized by NMR and vibrational spectroscopy, elemental analysis, and single-crystal X-ray diffraction. The reduction of the cyanoborane adducts has been investigated by cyclic voltammetry and the Lewis acidity of the different cyanoboranes has been assessed using the Gutmann-Beckett method. Selected experimental data and trends are compared to theoretical ones, for example fluoride ion affinities (FIAs). 相似文献