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71.
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
72.
Eberhard Bothe Helmut Gorner Joachim Opitz Dietrich Schulte-Frohlinde Aslam Siddiqi Malgorzata Wala 《Photochemistry and photobiology》1990,52(5):949-959
Double-stranded (ds) calf thymus DNA (0.4 mM), excited by 20 ns laser pulses at 248 nm, was studied in deoxygenated aqueous solution at room temperature and pH 6.7 in the presence of a sodium salt (10 mM). The quantum yields for the formation of hydrated electrons (phi c-), single-strand breaks (phi ssb) and double-strand breaks (phi dsb) were determined for various laser pulse intensities (IL). phi c- and phi ssb increase linearly with increasing IL; however, phi ssb has a tendency to reach saturation at high IL (greater than 5 X 10(6) Wcm-2). The ratio phi ssb/phi c-, representing the number of ssb per radical cation, is about 0.08 at IL less than or equal to 5 X 10(6) Wcm-2. For comparison, the number of ssb per OH radical reacting with dsDNA is 0.22. On going from argon to N2O saturation, phi ssb and phi dsb become larger by factors of approximately 5 and 10-15, respectively. This enhancement is produced by attack on DNA bases by OH radicals generated by N2O-scavenging of the photoelectrons. While phi ssb is essentially independent of the dose (Etot), phi dsb depends linearly on Etot in both argon- and N2O-saturated solutions. The linear dependence of phi dsb implies a square dependence of the number of dsb on Etot. This portion of dsb formation is explained by the occurrence of two random ssb, generated within a critical distance (h) in opposite strands. For both argon- and N2O-saturated solutions h was found to be of the order of 40-70 phosphoric acid diester bonds. On addition of electron scavengers such as 2-chloroethanol (or N2O plus t-butanol), phi dsb is similar to that in neat, argon-saturated solutions. Thus, hydrated electrons are not involved in the chemical pathway leading to laser-pulse-induced dsb of DNA. 相似文献
73.
Emilie Barriau Holger Frey Anton Kiry Manfred Stamm Franziska Gröhn 《Colloid and polymer science》2006,284(11):1293-1301
The preparation of carboxylated hyperbranched polyglycerols of narrow polydispersity was achieved by modification (78–90%) of the hydroxyl end groups via Michael addition of acrylonitrile, followed by hydrolysis. High conversion could only be achieved for low molecular weight starting materials (520 and 1,030 g mol−1). The solution properties of the resulting materials were investigated by dynamic light scattering (DLS), showing the formation of large aggregates with size depending on the pH value. After deposition on a negatively charged mica surface, the structures observed by atomic force microscope (AFM) show the coexistence of aggregates and single macromolecules. Most interesting, in the case of the lower molecular weight sample (PG 520 g mol−1), extended and ordered terrace structures were formed, which are unprecedented for hyperbranched polymers and are of interest for surface modification in general. 相似文献
74.
Dilatometrical indication can be employed to the neutralizing reactions of polybasic acids and is demonstrated by the following acid-base couples: H2SO4/NaOH, H3PO4/NaOH and H5JO6/NaOH. With amounts between 0.5 and 4 mMol several, frequently all, equivalence points can be determined with a deviation of less than 0.2%. The determination of the changes of molar volume of the reactions depending on the concentrations allow conclusions as to the course of the reactions. 相似文献
75.
Preparation of β-hydroxyesters from isoxazolines. A selective Nibpy-catalyzed electrochemical method
Viviane F. CaetanoF.W.Joachim Demnitz Flamarion B. DinizRonaldo M. Mariz Jr. Marcelo Navarro 《Tetrahedron letters》2003,44(45):8217-8220
An electrocatalytic method for the reductive N-O cleavage of isoxazolines is described. Ni0bpy, generated in situ, was used to promote selective ring opening of 3-methoxy-5-phenylisoxazoline (1a) and 3-methoxy-[4,5]cyclohexylisoxazoline (1b). DMF and NaI were used as solvent and supporting electrolyte, and β-hydroxyesters 2a and 2b were obtained in high yields respectively, after acid hydrolysis. β-Hydroxynitriles 3a and 3b were also identified as side products. 相似文献
76.
Gröger H Hummel W Buchholz S Drauz K Nguyen TV Rollmann C Hüsken H Abokitse K 《Organic letters》2003,5(2):173-176
[reaction: see text] An enzyme-compatible biphasic reaction media for the asymmetric biocatalytic reduction of ketones with in situ cofactor regeneration has been developed. In this biphasic reaction media, which is advantageous for reactions at higher substrate concentrations, both enzymes (alcohol dehydrogenase and FDH from Candida boidinii) remain stable. The reductions with poorly water-soluble ketones were carried out at substrate concentrations of 10-200 mM, and the optically active (S)-alcohols were formed with moderate to good conversions and with up to >99% ee. 相似文献
77.
Friedrich J Dolg M Gansäuer A Geich-Gimbel D Lauterbach T 《Journal of the American Chemical Society》2005,127(19):7071-7077
The mechanism of titanocene mediated 3-exo cyclizations was investigated by a combined theoretical and experimental study. A gradient corrected density functional theory (DFT) method has been scaled against titanocene dichloride, the parent butenyl radical, and in bond dissociation energy (BDE) calculations. The BP86 method using density fitting, and a basis set of triple-zeta quality emerged as a highly reliable tool for studying titanocene mediated radical reactions. The computational results revealed important kinetic and thermodynamic features of cyclopropane formation. Surprisingly, the beta-titanoxy radicals, the first intermediates of our investigations, were demonstrated to possess essentially the same thermodynamic stabilization as the corresponding alkyl radicals by comparison of the calculated BDEs. In contrast to suggestions for samarium mediated reactions, the cyclization was shown to be thermodynamically favorable in agreement with earlier kinetic studies. It was established that stereoselectivity of the cyclization is governed by the stability of the intermediates and thus the trans disubstituted products are formed preferentially. The observed ratios of products are in good to excellent agreement with the DFT results. By a combination of computational and experimental results, it was also shown that for the completion of the overall cyclopropane formation the efficiency of the trapping of the cyclopropylcarbinyl radicals is decisive. 相似文献
78.
Izilda A. Bagatin Alexandre T. Cruz Henrique E. Toma Mário J. Politi Grégoire J. -F. Demets 《Journal of inclusion phenomena and macrocyclic chemistry》2005,52(3):189-193
This article reports the synthesis and the properties of 5,11,17,23-tetra(t-butyl)-25,27-bis-(ethoxy-1,8-naphthalimide)-26,28-hidroxy-calix[4]arene and the formation of an inclusion compound in organic medium. This functionalized calix[4]arene was conceived as the association of a potential host species with a good fluorophore for optical sensoring purposes. Calix[4]-NI as we will call it, maintains its ‘cone-pinched’ configuration and exhibits typical naphthalimide fluorescence bands in non-polar solvents. Its ability to interact with guest species via hydrogen bonding in its endo-hydrophilic cavity to form inclusion compounds was verified with absorption and fluorescence measurements using N-ethanol-1,8-naphthalimide as guest species, which was projected to fit exactly the host cavity and to interact with its naphthalimide π electrons. For this reason, it was possible to follow the formation of the inclusion compound with electronic spectroscopy. 相似文献
79.
Lili Hu Marcus Wolf Michael Grätzel Zhonghong Jiang 《Journal of Sol-Gel Science and Technology》1995,5(3):219-226
The hydrolysis of niobium pentaethoxide precursor in the presence of triethylamine (TEA) is discussed. Three precursors with TEA/Nb(OEt)5 mole ratios of 0.25, 0.4 and 0.8 were prepared. Niobia colloids with different appearance were obtained after autoclaving the above precursors at 250°C during 12 h. The surface roughness and microstructure of niobia films prepared with the colloids by spread coating method are strongly dependent on the TEA/Nb(OEt)5 mole ratio. At a value of 0.4 TEA/Nb(OEt)5 mole ratio, a niobia film with large surface roughness can be achieved. It is opaque and mechanically stable and has differently ordered needle microstructure. The crystalline structure and photoelectrochemical property of niobia film with the largest surface roughness were examined. The effect of CO2 gas bubbling, reflux and addition of 2-methoxyethanol on the hydrolysis of Nb(OEt)5 and the nature of the Nb2O5 films is also discussed. 相似文献
80.
Iron-silicon thin films have been characterized by means of analytical transmission electron microscopic methods. Under certain conditions — composition and annealing temperature — these films exhibit thermoelectric behavior. In particular, the morphology and phase formation which results from annealing of these films, and doping with oxygen and nitrogen, are of interest. The thermoelectric phase -FeSi2 is formed at temperatures above 500°C. This phase is transformed into electrically conducting phases at about 1000°C. A small oxygen content does not influence this crystallization process. If the oxygen content is higher than 15 atom-% the electrically conducting phases exist even at 500°C. The presence of a small nitrogen content inhibits the formation of the -FeSi2 phase. The development of silicon and iron nitrides is possible. 相似文献