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51.
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Steinmetz H Irschik H Kunze B Reichenbach H Höfle G Jansen R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(20):5822-5832
Two novel antibiotics, thuggacin A (1) and B (2), were isolated from the myxobacterium Sorangium cellulosum. 1 and 2 are unique thiazole-containing macrolides with side chains on both sides of the lactone group. Upon standing in solution, thuggacin A (1) rearranges by acyl migration of the lactone group to give a mixture with thuggacins B (2) and C (3). NOEs and vicinal coupling constants within the lactone ring provided distinct data for the generation of a structure model by PM3 calculations, which allowed an analysis of the conformation in solution and the relative configuration of six asymmetric centres. A minor sorangium metabolite was identified as 13-methyl-thuggacin A (4). Furthermore, two natural thuggacin variants, 5 and 6, were found in another myxobacterium, Chondromyces crocatus. In these variants, one side chain is replaced by a methyl group and a hydroxy group is repositioned to give a primary alcohol at the former methyl site, in an alpha position with respect to the thiazole ring. 1 proved to be active against clinical isolates and reference strains of Mycobacterium tuberculosis. Preliminary studies on the mechanism of action indicate inhibition of the cellular electron-transport chain. 相似文献
53.
Investigations on the activation of cellulose by mixed solutions of caustic soda and urea are reported. The structural effects of those solutions on various dissolving pulps are studied by 13C-CP/MAS-NMR spectroscopy. In a series of steeping lyes, the concentration of NaOH was varied in a range from 0% to 8% and the urea-concentration in a range from 15% to 40% at ambient temperature and −25 °C. Using solely the single NaOH or urea solutions in the concentration ranges given above, no or only minor structural changes were found. In contrast to that, the cellulose I structure was partially or completely destroyed by using the bicomponent solution with urea added to caustic soda. The structural effect of the bicomponent solutions is comparable with the effect of solely caustic soda solutions of approx. 10% to 18% NaOH. However, the 13C-CP/MAS-NMR-spectra from the bicomponent pretreated samples indicate a structure different from the usual ordered structures of sodium cellulose I or II, namely a special urea-NaOH-cellulose complex. The results show that for cellulose activation the NaOH concentration of the caustic soda can be remarkably reduced by adding urea. The improved activating effect of an optimized caustic soda solution with added urea was proved to be useful for the synthesis of cellulose carbamate. 相似文献
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Kunze J Leitch J Schwan AL Faragher RJ Naumann R Schiller S Knoll W Dutcher JR Lipkowski J 《Langmuir : the ACS journal of surfaces and colloids》2006,22(12):5509-5519
For a monolayer of 2,3-di-phytanyl-sn-glycerol-1-tetraethylene glycol-D,L-a-lipoic acid ester lipid (DPTL) self-assembled (SAM) at a gold electrode surface we propose a new method to determine the charge number per adsorbed molecule and the packing density (area per molecule) in the monolayer. The method relies on chronocoulometry to measure the charge density at the SAM covered gold electrode surface. Two series of measurements have to be performed. In the first series, charge densities are measured for a monolayer transferred from the air-solution to the metal-solution interface using the Langmuir-Blodgett (LB) technique. This series of measurements allows one to determine charge numbers per adsorbed DPTL molecule. The second series is performed using a gold electrode covered with a self-assembled monolayer. The charge densities obtained in this series are then used to calculate the packing density with the help of charge numbers per adsorbed DPTL determined in the first series. The area per adsorbed molecule determined by the new method was compared to the area per molecule determined by the popular reductive desorption method. The molecular area determined with the new method is about 20% larger than the area calculated from the van der Waals model, which is a physically reasonable result. In contrast, the popular reductive desorption method gives an area per molecule 20% lower than the minimum estimated based on a van der Waals model. This is a physically unreasonable result. It is also shown that the charge numbers per adsorbed molecule depend on the electrode potential and may assume values smaller than the number of electrons participating in the reductive desorption step. An explanation of the origin of the "partial charge numbers" is provided. We recommend the new method be used in future studies of thiol adsorption at metal surfaces. 相似文献
57.
König AM Düwel M Du B Kunze M Johannsmann D 《Langmuir : the ACS journal of surfaces and colloids》2006,22(1):229-233
We discuss the influence of a limited contact size on measurements of high-frequency interfacial viscoelasticity performed with a combination of a quartz crystal microbalance (QCM) and the Johnson-Kendall-Roberts (JKR) apparatus. In this instrument, a sphere-plate contact is established between an elastomeric lens and a quartz resonator. The analysis is carried out in the frame of the sheet-contact model, which states that both the shift of resonance frequency and the bandwidth are proportional to the contact area as long as the contact area is much smaller than the crystal itself. In particular, the ratio of the shift in bandwidth and the shift in frequency (termed the D-f ratio) is predicted to be constant and independent of geometry. However, the experiment does show a slight increase in the D-f ratio with the contact radius when the contact radius is comparable to the wavelength of sound inside the crystal. This effect can be explained by acoustic scattering. 相似文献
58.
G Höfle K Gerth H Reichenbach B Kunze F Sasse E Forche EV Prusov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(36):11362-11370
Eliamid is a secondary metabolite isolated from two bacterial strains. This molecule features a linear polyketide backbone terminated by a tetramic acid amide moiety. Among other biological activities, eliamid shows a high and specific cytostatic action on human lymphoma and cervix carcinoma cell lines. The 2,4-anti relative configuration of the C-2,C-4-dimethyl substituted amide fragment was assigned by means of Breit's rule. The absolute configuration of all stereocenters was determined by a combination of degradation methods, structural similarity analysis and total synthesis. The stereogenic centers were introduced by vinylogous Mukaiyama aldol reaction and two consecutive Myers alkylations. The use of pentafluorophenyl ester as acylation agent allowed the efficient formation of tetramic acid amide. The longest linear sequence in the synthesis consist of 13?steps and proceeds with 12?% overall yield. Differential spectroscopy experiments with beef heart submitochondrial particles established that eliamid is a potent inhibitor of the NADH-ubiquinone oxidoreductase complex. Additionally, biosynthesis of eliamid was investigated by feeding experiments with (13) C-labeled precursors. 相似文献
59.
G. Kunze 《Crystal Research and Technology》1975,10(2):175-199
The quantity of the shear-modulus G′ = (c11 – c12)/2 is a measure for the probability of structural Umklapp-processes to occur in metastable β1-Cu-Zn-solid solutions. Such processes take place, if G′ = G′(T, x) would fall below a critical limit, G′crit, e.g. by lowering of temperature T or/and Zn-concentration x, because the Fermi-contribution to G′will sink in the 1st and with him additional the Coulomb-contribution in te 2nd case. Both ones are the authoritative stabilizing factors for β1 and therefore specific fo its lattice-dynamical behaviour, especially in the longwavy range of thermoacoustic lattice-vibrations, by which the cooperative Umklapp-motion will escape. Umklapping can also be initiated by favourably oriented dislocations, is G′ would approach to G′crit in their neighbourhood: G′critG′(xM8), with xM8 Umklapp-concentration. This is possible by variation of x during isothermal reactions, in the course of whicht he β1-matrix will heterogenize itself into Zn-poorer and -richer districts β and β (pre-diffusion by means of quenchy vacancies). Both kinds of districts, among which the latter ones will enhance their degree of stability, are joint together coherently. They build up a so called β /β -parquet. The parquet-bricks can reach a critical size, which is necessary that sufficient large atom-collectives can simultaneously be caused to an Umklapp-motion and to occupate new equilibrium positions by thermo-acoustic shear-waves (comparison with a sin-wave beeing changed to a zigzag-line). Only at higher temperatures the bricks come up to the critical size. Umklapping comes about only in the β -bricks, which turn by it to a transition lattice (β2) with a structure similary to that of the lowtemperature-martensite β′′. After that β2 changes to α-phase. The way β ⇒ α is marked by the following steps: prediffusion, Umklapping + dislocation, leading to β2, and a further dislocation dissoziation, leading the atoms to the equilibrium positions in the α-lattice. The so stepped mechanism acts an nucleationmechanism of the α-phase. After the nucleation the α-nuclei grow at the cost of too much formed β (postdiffusion). By isothermal reactions at too low temperatures a mini-herterogenized state of the β1-matrix will be caused comparable with coldhardening states of other alloys (Guinier-Preston-zones). A β1-matrix in such a state is unable to isothermal Umklapping, so that α-crystals can be formed – provided that the mini-heterogenities are resolved by increasing of the reaction temperature. 相似文献
60.