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Efforts are described to design simple, fully flexible but conformationally preorganised omega-hydroxy-nonanoic acids that could serve as the conformation controlling unit in analogues of the potent protein-kinase C activator aplysiatoxin. Such analogues are macrodilactones incorporating the designed omega-hydroxy-nonanoic acid and 3,4-dihydroxy-pentanoic acid, which contains the pharmacophoric groups. The design process (replacement of CH(2) groups by an oxygen atom, annelation of a six-membered ring and placement of alkyl substituents) of the omega-hydroxy-nonanoic acids was monitored by force-field calculations. In the end of this process simple analogues of aplysiatoxin are proposed in which the proper disposition of the pharmacophoric groups is secured by a conformationally flexible but preorganised template structure as part of the macrodilactone ring. 相似文献
3.
[structure: see text] By relying on the asymmetric aldol reactions of chiral ketones, a highly stereocontrolled synthesis of each of the C(17)-C(22) and C(23)-C(35) degradation fragments of reidispongiolide A has been achieved. This permits a configurational assignment of the complete C(17)-C(36) region of this antimitotic macrolide, along with providing advanced intermediates for a projected total synthesis. 相似文献
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Eva C. Sonnenschein Marc Stierhof Stephan Goralczyk Floriane M. Vabre Leonie Pellissier Kine Østnes Hanssen Mercedes de la Cruz Caridad Díaz Peter de Witte Daniëlle Copmans Jeanette Hammer Andersen Espen Hansen Venke Kristoffersen José R. Tormo Rainer Ebel Bruce F. Milne Hai Deng Lone Gram Jioji N. Tabudravu 《Tetrahedron》2017,73(18):2633-2637
A new siderophore containing a 4,5-dihydroimidazole moiety was isolated from Pseudoalteromonas piscicida S2040 together with myxochelins A and B, alteramide A and its cycloaddition product, and bromo- and dibromoalterochromides. The structure of pseudochelin A was established by spectroscopic techniques including 2D NMR and MS/MS fragmentation data. In bioassays selected fractions of the crude extract of S2040 inhibited the opportunistic pathogen Pseudomonas aeruginosa. Pseudochelin A displayed siderophore activity in the chrome azurol S assay at concentrations higher than 50 μM, and showed weak activity against the fungus Aspergillus fumigatus, but did not display antibacterial, anti-inflammatory or anticonvulsant activity. 相似文献
6.
Jun.-Prof. Dr. Max M. Hansmann Patrick W. Antoni Henner Pesch 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(14):5831-5836
We report a new class of stable mesoionic N-heterocyclic olefins, featuring a highly polarized (strongly ylidic) double bond. The ground-state structure cannot be described through an uncharged mesomeric Lewis-structure, thereby structurally distinguishing them from traditional N-heterocyclic olefins (NHOs). mNHOs can easily be obtained through deprotonation of the corresponding methylated N,N′-diaryl-1,2,3-triazolium and N,N′-diaryl-imidazolium salts, respectively. In their reactivity, they represent strong σ-donor ligands as shown by their coordination complexes of rhodium and boron. Their calculated proton affinities, their experimentally derived basicities (competition experiments), as well as donor abilities (Tolman electronic parameter; TEP) exceed the so far reported class of NHOs. 相似文献
7.
Mihlbachle K Jupke A Seidel-Morgenstern A Schmidt-Traub H Guiochon G 《Journal of chromatography. A》2002,944(1-2):3-22
Previous studies of the simulated moving bed (SMB) process assume identical characteristics of all the columns incorporated in a given unit. Due to the practical impossibility to manufacture identical columns, numerical applications of the theory to modeling and optimization use for each of the needed column parameter the average value for the entire column set. In this study, the effects of these simplifications on the actual productivity of the SMB process are evaluated by making exact calculations, i.e., by taking the differences in the porosity values into account. We apply a revised set of separation conditions previously introduced and derived from the equilibrium theory. Earlier theoretical results are compared to experimental results obtained in the study of the enantiomeric separation of Tr?ger's base on Chiralpak AD. Due to the nonLangmuirian character of the adsorption isotherms of these two compounds on the packing material used, the separation area cannot be determined analytically. As an alternative, a reliable numerical algorithm was used to scan a wider region and to define the separation area. The form of this area depends on the applied porosity values. A UV detector and a laser polarimeter located at one node of the SMB monitor on-line the internal concentration profiles. Excellent agreement between the calculated and the experimentally determined concentration profiles was obtained under nonlinear conditions. The influence of column-to-column variations on the performance of the SMB process was found to be more significant under nonlinear than under linear conditions. 相似文献
8.
Bréchignac C Cahuzac P Concina B Leygnier J Ruiz LF Zarour B Hervieux PA Hanssen J Politis MF Martín F 《Physical review letters》2002,89(18):183402
We present a combined theoretical and experimental study of charge transfer and dissociation in collisions of slow Li31(2+) clusters with Cs atoms. We provide a direct quantitative comparison between theory and experiment and show that good agreement is found only when the exact experimental time of flight and initial cluster temperature are taken into account in the theoretical modeling. We demonstrate the validity of the simple physical image that consists in explaining evaporation as resulting from a collisional energy deposit due to cluster electronic excitation during charge transfer. 相似文献
9.
Capacchione C Proto A Ebeling H Mülhaupt R Möller K Spaniol TP Okuda J 《Journal of the American Chemical Society》2003,125(17):4964-4965
Styrene is polymerized isospecifically by group 4 metal complexes that contain a C2-symmetrically coordinated 1,4-dithiabutane-linked bis(phenolato) ligand activated by methylaluminoxane. 相似文献
10.
A spectrophotometer system for spectral characterization of materials in the infrared has been built around a bench-top Fourier transform instrument. Its capabilities include the measurement of directional-hemispherical reflectance from 1 to 18 μm. The spectral reflectance measurement is performed with an integrating sphere with an incidence angle of 8°. Both relative and absolute measurements can be made. Several methods can be used to determine the absolute value of the directional-hemispherical reflectance of samples. The primary method used is independent of the integrating sphere theory and the requisite assumptions associated with its use. The calibration of a standard reference material (SRM) is described. This SRM has a reflectance value near 0.9 over the complete calibration range 2–18 μm. As part of the calibration procedure the spatial uniformity of the sphere throughput and the bi-directional reflectance distribution function (BRDF) of the SRM material are evaluated. 相似文献