Chartreusin is a potent antitumor agent with a mixed polyketide-carbohydrate structure produced by Streptomyces chartreusis. Three type II polyketide synthase (PKS) gene clusters were identified from an S. chartreusis HKI-249 genomic cosmid library, one of which encodes chartreusin (cha) biosynthesis, as confirmed by heterologous expression of the entire cha gene cluster in Streptomyces albus. Molecular analysis of the approximately 37 kb locus and structure elucidation of a linear pathway intermediate from an engineered mutant reveal that the unusual bis-lactone aglycone chartarin is derived from an anthracycline-type polyketide. A revised biosynthetic model involving an oxidative rearrangement is presented. 相似文献
The results of all-electron density functional calculations on the bimetallic cluster compounds [M(4){Fe(CO)(4)}(4)](4-) (M = Cu, Ag, Au) and on the corresponding naked species M(4)Fe(4) are reported. The trends within the triad have been investigated. The bare metal clusters exhibit a strong magnetization which is quenched on addition of CO ligands. The bonding in the bare clusters is different for the silver derivative compared to that of copper and gold, resulting in comparatively weaker Ag-Fe and Ag-Ag bonds. This can be rationalized in terms of the different d-sp mixing, which for Cu and Au is larger than for Ag. Relativistic effects act to increase the 4d-5s mixing in Ag and to strengthen the intermetallic bond with Fe. In the carbonylated clusters a charge transfer from the metal M (M = Cu, Ag, or Au) to the Fe(CO)(4) groups occurs so that the atoms M can be considered in a formal +I oxidation state, rationalizing the nearly square-planar geometry of the metal frame. In fact, the local coordination of the M atoms is almost linear, as expected for complexes of M(I). The addition of extra electrons results in a stabilization of the clusters, indicating the electron-deficient nature of these compounds. Similar features have been found for the largest cluster synthesized so far for this class of compounds, [Ag(13){Fe(CO)(4)}(8)](n)(-), (n = 0-5). The nature and localization of the unpaired electron in the tetraanion is also discussed. 相似文献
It is common practice to base investment decisions on price projections which are gained from simulations using price processes. The choice of the underlying process is crucial for the simulation outcome. For power plants the core question is the existence of stable long-term cointegration relations. Therefore we investigate the impacts of different ways to model price movements in a portfolio selection model for the German electricity market. Three different approaches of modelling fuel prices are compared: initially, all prices are modelled as correlated random walks. Thereafter the coal price is modelled as random walk. The gas price follows the coal price through a mean-reversion process. Lastly, all prices are modelled as mean reversion processes with correlated residuals. The prices of electricity base and peak futures are simulated using historical correlations with gas and coal prices. Yearly base and peak prices are transformed into an estimated price duration curve followed by the steps power plant dispatch, operational margin and net present value calculation and finally the portfolio selection. The analysis shows that the chosen price process assumptions have significant impacts on the resulting portfolio structure and the weights of individual technologies. 相似文献
The perceptual-cognitive mechanisms and neural correlates of Absolute Pitch (AP) are not fully understood. The aim of this
fMRI study was to examine the neural network underlying AP using a pitch memory experiment and contrasting two groups of musicians
with each other, those that have AP and those that do not. 相似文献
Charge reversal (+CR−) of cations to anions can be used to structurally differentiate isomeric C6H5+ and C6H6+· hydrocarbon ions by means of tandem mass spectrometry. In view of the manifold of possible isomers, only a few prototype precursors are examined. Thus, charge inversion demonstrates that electron ionization of 2,4-hexadiyne yields an intact molecular ion, whereas the charge inversion spectra of C6H6+· obtained from benzene, 1,5-hexadiyne, and fulvene are identical within experimental error. Similarly, the +CR− spectrum of the C6H5+ cation generated by dissociative ionization of 2,4-hexadiyne is significantly different from the +CR− spectrum of C6H5+ obtained from iodobenzene, suggesting the formation of a 2,4-hexadiynyl cation from the former precursor. Although charge inversion of cations to anions has a low efficiency and requires large precursor ion fluxes, the particular value of this method is that the spectra may not just differ in fragment ion intensities, but these differences can directly be related to the underlying ion structures. 相似文献
In this study, two different synthetic methods in aqueous solution are presented to tune the optical properties of CdTe and CdSe semiconductor nanoparticles. Additionally, the influence of different temperatures, pressures, precursor ratios, surface ligands, bases, and core components in the synthesis was investigated with regard to the particle sizes and optical properties. As a result, a red shift of the emission and absorption maxima with increasing reaction temperature (100 to 220°C), pressure (1 to 25 bar), and different ratios of core components of alloyed semiconductor nanoparticles could be observed without a change of the particle size. An increase in particle size from 2.5 to 5 nm was only achieved by variation of the mercaptocarboxylic acid ligands in combination with the reaction time and used base. To get a first hint on the cytotoxic effects and cell uptake of the synthesized quantum dots, in vitro tests mesenchymal stem cells (MSCs) were carried out.
