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Wagner F Gruber O Lackner K Murmann HD Speth E Becker G Bosch HS Brocken H Cattanei G Dorst D Eberhagen A Elsner A Erckmann V Fussmann G Gehre O Gernhardt J Gierke Gv Glock E Grieger G Grigull P Haas G Hacker H Hartfuss HJ Jäckel H Jaenicke R Janeschitz G Junker J Karger F Kasparek W Keilhacker M Kick M Klüber O Kornherr M Kroiss H Kuehner M Lenoci M Lisitano G Maassberg M Mahn C Marlier S Mayer HM McCormick K Meisel D Mertens V Müller ER Müller Müller G Niedermeyer H Ohlendorf W 《Physical review letters》1986,56(20):2187-2190
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[reaction: see text] The fluorescence quenching of 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) by nucleotides has been studied. The quenching mechanism was analyzed on the basis of deuterium isotope effects, tendencies for exciplex formation, and the quenching efficiency in the presence of a molecular container (cucurbit[7]uril). Exciplex-induced quenching appears to prevail for adenosine, cytidine, and uridine, while hydrogen abstraction becomes competitive for thymidine and guanosine. Compared to other fluorescent probes, DBO responds very selectively to the type of nucleotide. 相似文献
26.
By use of salt elimination, the transition metal substituted oligosilanes (η5-C5Me4Et)Fe(CO)2SiMe2SiMe2Cl 1, (η5-C5Me4Et)Mo(CO)3SiMe2SiMe2Br 2, (η5-C5Me4Et)Fe(CO)2(SiMe2)6(CO)2Fe(η5-C5Me4Et) 3 and (η5-C5Me4Et)Fe(CO)2(SiMe2)6Br 4 were prepared and characterized. Compound 1 is well crystallized from pentane and its structure has been determined by X-ray diffraction analysis. 相似文献
27.
The interaction of an excess electron with a polar molecular environment is well known as electron solvation. This process is characterized by an energetic stabilization and by changes of the electronic spatial extent due to screening of the localized charge through molecular rearrangement. At metal–ice interfaces we photo-inject delocalized electrons from the metal substrate into adsorbed ice layers and analyze the ultrafast dynamics of electron transfer, localization and solvation by femtosecond time- and angle-resolved two-photon photoemission spectroscopy. To acquire further understanding of the individual steps of the complex process we vary the interfacial structure. The substrate is changed between Cu(1 1 1) and Ru(0 0 1) and the electron dynamics in ice islands are compared to closed D2O layers. Contrasting crystalline and amorphous ice we found that electron solvation is mediated through electron localization at favorable structural sites, which occurs very efficiently in amorphous ice, but is less likely in a crystalline layer. Next, we find that in an open ice structure like ice islands the energetic stabilization due to electron solvation proceeds at a rate of 1 eV/ps which is three times faster than in a closed ice layer. We attribute this behavior to differences in the molecular coordination, which determines the molecular mobility and, thus, the transfer rate of electronic energy to solvent modes. The substrate’s electronic structure, on the other hand, is important to understand the transfer rates from electrons in ice back to the metal. First experiments on trapped electrons in crystalline ice underline the potential to study electron solvation not only during the equilibration process, but also in quasi-static conditions, where we find that the stabilization continues, although at much weaker rates. 相似文献
28.
Heterobimetallic Phosphanido-bridged Dinuclear Complexes - Syntheses of cis-rac-[(η-C5H4R)2Zr{μ-PH(2,4,6-iPr3C6H2)}2M(CO)4] (R?Me, M?Cr, Mo; R?H, M?Mo) The zirconocene bisphosphanido complexes [(η-C5H4R)2Zr{PH(2,4,6-iPr3C6H2)}2] (R?Me, H) react with [(NBD)M(CO)4] (NBD?norbornadiene, M?Cr, Mo) to give only one diastereomer of the phosphanido-bridged heterobimetallic dinuclear complexes cis-rac-[(η-C5H4R)2Zr{μ-PH(2,4,6-iPr3C6H2)}2M(CO)4] [R?Me, M?Cr ( 1 ), Mo ( 2 ); R?H, M?Mo ( 3 )]. However, no reaction was observed between [(η-C5H5)2Zr{PH(2,4,6-tBu3 C6H2)}2] and [Pt(PPh3)4]. 1—3 were characterised spectroscopically. For 1—3 , the presence of the racemic isomer was shown by NMR spectroscopy. No reaction was observed at room temperature for 3 and CS2, (NO)BF4, Me3NO or PH(2,4,6-Me3C6H2)2. With Et2AlH or PhC?CH decomposition of 3 was observed. 相似文献
29.
Synthesis and derivatization of daptomycin: a chemoenzymatic route to acidic lipopeptide antibiotics
Grünewald J Sieber SA Mahlert C Linne U Marahiel MA 《Journal of the American Chemical Society》2004,126(51):17025-17031
Daptomycin is a branched cyclic nonribosomally assembled acidic lipopeptide, which is the first clinically approved antibiotic of this class. Here we show that the recombinant cyclization domain of the Streptomyces coelicolor calcium-dependent antibiotic (CDA) nonribosomal peptide synthetase (NRPS) is a versatile tool for the chemoenzymatic generation of daptomycin derivatives. Linear CDA undecapeptide thioesters with single exchanges at six daptomycin-specific residues were successfully cyclized by CDA cyclase. Simultaneous incorporation of all six of these residues into the peptide backbone and elongation of the N-terminus of CDA by two residues yielded a daptomycin derivative that lacked only the beta-methyl group of l-3-methylglutamate. Bioactivity studies with several substrate analogues revealed a significant role of nonproteinogenic constituents for antibacterial potency. In accordance with acidic lipopeptides, the bioactivity of the chemoenzymatic assembled daptomycin analogue is dependent on the concentration of calcium ions. Single deletions of the four acidic residues in the peptide backbone suggest that only two aspartic acid residues are essential for antimicrobial potency. These two residues are strictly conserved among other nonribosomal acidic lipopeptides and the EF-motif of ribosomally assembled calmodulin. Based on these findings CDA cyclase is a versatile catalyst that can be used to generate novel daptomycin derivatives that are otherwise difficult to obtain by chemical modification of the parental tridecapeptide to improve further its therapeutic activity. 相似文献
30.
Uwe EilitzChristoph Böttcher Lothar HennigAlois Haas Cecile BoyerKlaus Burger 《Journal of fluorine chemistry》2002,115(2):149-154
Homochiral 2-C-perfluoroalkyl substituted d- and l-riboses were synthesized via Barbier, Grignard and Ruppert type reactions. The influence of the size of the perfluoroalkyl groups, attached to C-2, on the furanose/pyranose as well as on the α-furanose/β-furanose and α-pyranose/β-pyranose ratio in solution was studied. 相似文献