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Minjuan Xu Dr. Torsten Bruhn Dr. Barbara Hertlein Reto Brun Prof. Dr. August Stich Dr. Jun Wu Dr. Gerhard Bringmann Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(14):4206-4216
Five novel dimeric naphthylisoquinoline alkaloids, shuangancistrotectorines A ( 3 a ), B ( 3 b ), C ( 4 ), D ( 5 a ), and E ( 5 b ), have been isolated from the twigs of the Chinese plant Ancistrocladus tectorius. Their absolute stereostructures were determined by spectroscopic and chiroptical methods in combination with quantum chemical CD calculations. In contrast to all other known dimeric naphthylisoquinoline alkaloids, in which the central binaphthalene axis is 6′,6′′‐coupled and thus not rotationally hindered, the dimers described here are linked via the sterically more hindered 3′,3′′‐ or 1′,1′′‐positions of the naphthalene units. They are thus the first such dimers—and even the very first natural products at all—that have three consecutive stereogenic axes. Hence, including the stereogenic centers, they have up to seven stereogenic units in total. Some of the compounds, in particular shuangancistrotectorines A, B, and D ( 3 a , 3 b , and 5 a ) exhibit very good, and specific, antiplasmodial activities. 相似文献
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Reto Glaus Ralf Kaegi Frank Krumeich Detlef Günther 《Spectrochimica Acta Part B: Atomic Spectroscopy》2010,65(9-10):812-822
In laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS), the properties of laser-generated aerosols, such as size and composition, are crucial for matrix-independent quantification. In this study, the aerosol particle morphology and elemental composition generated by two state-of-the-art laser systems (ArF excimer nanosecond-UV laser and Ti:sapphire femtosecond-IR laser) were investigated by electron microscopic techniques. Electrostatic sampling of the aerosols directly onto transmission electron microscopy (TEM) grids allowed us to study the morphology and elemental composition of the aerosols using TEM and TEM–EDX (energy dispersive X-ray spectroscopy) analyses, respectively. The results of the electron microscopic studies were finally compared to the LA-ICPMS signals of the main matrix components. The investigations were carried out for non-conducting materials (glass and zircon), metallic samples (steel and brass) and semiconductors (sulfides). The studies confirm that ns-LA-generated aerosols dominantly consist of nanoparticle agglomerates while conducting samples additionally contain larger spherical particles (diameter typically 50 to 500 nm). In contrast to ns-laser ablation, fs-LA-generated aerosols consist of a mixture of spherical particles and nanoparticle agglomerates for all investigated samples. Surprisingly, the differences in elemental composition between nanoparticle agglomerates and spherical particles produced with fs-LA were much more pronounced than in the case of ns-LA, especially for zircon (Si/Zr fractionation) and brass (Cu/Zn fractionation). These observations indicate different ablation and particle formation mechanisms for ns- and fs-LA. The particle growth mechanism for ns-LA is most likely a gas-to-particle conversion followed by agglomeration and additional hydrodynamic sputtering for conducting samples. On the other hand, phase explosion is assumed to be responsible for the mixture of large spherical particles and nanoparticle agglomerates as found for fs-LA-generated aerosols. Based on these mechanisms, the overall temporal elemental fractionation effects in ns-LA-ICPMS seem to occur mainly during the ablation. This effect was not observed for fs-LA-ICPMS despite the element separation into different particle fractions, which, on the other hand, could induce severe ICP-induced fractionation. 相似文献
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Werner Seebacher Marcel Kaiser Reto Brun Robert Saf Robert Weis 《Monatshefte für Chemie / Chemical Monthly》2007,138(7):709-714
Summary. We synthesized several 4-aminobicyclo[2.2.2] octan-2-ols and 4-amino-2-azabicyclo[3.2.2]nonanes from epimerized 4-amino-bicyclo[2.2.2]octan-2-ones.
The new compounds were tested for their activity against Trypanosoma b. rhodesiense, the causative organism of East African sleeping sickness, and Plasmodium falciparum K
1, a multiresistant protozoan parasite which causes Malaria tropica. The results are compared to the activities of their formerly
synthesized stereoisomers and structure–activity relationships are discussed. 相似文献
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Gregory R. Lumpkin Katherine L. Smith Mark G. Blackford Reto Gier C. Terry Williams 《Micron (Oxford, England : 1993)》1994,25(6):581-587
In this paper we describe a technique for the determination of 25 elements in natural zirconolite using energy-dispersive analytical electron microscopy (AEM). The method presented here allows one to quantitatively investigate the chemistry of submicron-scale zones in complex oxide minerals. The effects of electron channeling, thickness variability and variations in detector resolution were minimized by using a controlled set of operating procedures and instrument parameters. To provide a high level of accurayy, kATI-factors were determined from standards for most of the 25 elements of interest, including all of the major elements. Each analytical spectrum is reduced to a set of raw peak counts (and errors) using a digital top-hat filter to suppress background followed by multiple least squares fitting of reference spectra. Counting times of 12–15 min per analysis were required to provide suitable counting statistics. Results are presented for zirconolite samples from the contact metamorphic aureole of the Bergell granodiorite intrusion, Switzerland-Italy. A comparison of 43 AEM analyses with 15 analyses obtained by wavelength-dispersive electron probe microanalysis (EPMA) shows that there is excellent agreement between the two data sets in the amounts of individual elements present, chemical trends and overall stoichiometry. An assessment of the combined data set shows that the major substitution mechanisms in the Bergell samples are coupled substitutions involving the M5,6- and M8-sites of the zirconolite structure: M8Ca2+ + M5,6Ti4+→M8REE3+ + M5,6(Al,Fe)3+ and M8Ca2+ + M5,6Ti4+→M8(Th,U)4+ + M5,6 (Mg,Fe)2+. 相似文献
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In structural biology, pulsed field gradient (PFG) NMR spectroscopy for the characterization of size and hydrodynamic parameters of macromolecular solutes has the advantage over other techniques that the measurements can be recorded with identical solution conditions as used for NMR structure determination or for crystallization trials. This paper describes two transverse-relaxation-optimized (TRO) (15)N-filtered PFG stimulated-echo (STE) experiments for studies of macromolecular translational diffusion in solution, (1)H-TRO-STE and (15)N-TRO-STE, which include CRINEPT and TROSY elements. Measurements with mixed micelles of the Escherichia coli outer membrane protein X (OmpX) and the detergent Fos-10 were used for a systematic comparison of (1)H-TRO-STE and (15)N-TRO-STE with conventional (15)N-filtered STE experimental schemes. The results provide an extended platform for evaluating the NMR experiments available for diffusion measurements in structural biology projects involving molecular particles with different size ranges. An initial application of the (15)N-TRO-STE experiment with very long diffusion delays showed that the tedradecamer structure of the 800 kDa Thermus thermophilus chaperonin GroEL is preserved in aqueous solution over the temperature range 25-60 °C. 相似文献
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Stump B Eberle C Kaiser M Brun R Krauth-Siegel RL Diederich F 《Organic & biomolecular chemistry》2008,6(21):3935-3947
Trypanothione reductase (TR) is an essential enzyme of trypanosomatids and therefore a promising target for the development of new drugs against African sleeping sickness and Chagas' disease. Diaryl sulfides with a central anilino moiety, decorated with a flexible N-alkyl side chain bearing a terminal ammonium ion, are a known class of inhibitors. Using computer modelling, we revised the binding model for this class of TR inhibitors predicting simultaneous interactions of the ammonium ion-terminated N-alkyl chain with Glu18 as well as Glu465'/Glu466' of the second subunit of the homodimer, whereas the hydrophobic substituent of the aniline ring occupies the "mepacrine binding site" near Trp21 and Met113. Systematic alteration of the carboxylate-binding fragments and the diaryl sulfide core of the inhibitor scaffold provided evidence for the proposed binding mode. In vitro studies showed IC(50) values in the low micromolar to submicromolar range against Trypanosoma brucei rhodesiense as well as the malaria parasite Plasmodium falciparum. 相似文献