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41.
Vidak Raičević Niko Radulović Ljiljana Jovanović Marko Rodić Ivana Kuzminac Dimitar Jakimov Tanja Wrodnigg Tim-Oliver Knedel Christoph Janiak Marija Sakač 《应用有机金属化学》2020,34(10):e5889
Conjugates of ferrocene with steroidal estrogens as selective antiproliferative agents against hormone-dependent breast cancer cells are believed to be limited by the inherent estrogenicity of the conjugates. Motivated by a significant cytotoxicity of the ester of ferrocenecarboxylic acid and the phenolic group of estradiol toward such a cell line, we decided to explore other a -ring-tethered ferrocene–estra-1,3,5(10)-triene conjugates; in this study, ferrocenylmethylation of estradiol and estrone with (ferrocenylmethyl)trimethylammonium iodide in the presence of potassium carbonate yielded five new compounds ( 1 – 5 ). In dimethylformamide, only O-alkylated products formed ( 1 and 3 ), while a mixture of O- and C-alkylated products was obtained when methanol was used ( 2 , 4 , and 5 in addition to 1 and 3 ). All compounds were characterized using 1D and 2D NMR, IR, UV–Vis, and high-resolution mass spectrometry. Two of the conjugates, a 3-O- and a 4-C-alkylated derivative of estrone ( 3 and 4 , respectively), were also analyzed using single-crystal X-ray diffraction. A cyclic voltammetric investigation of the electrochemical properties of 1 – 5 was performed. While some of the compounds were shown to have a slight-to-moderate antiproliferative activity against at least one of the six tested human tumor cell lines and were nontoxic to (the noncancerous) fetal human fibroblasts, compound 2 (4-(ferrocenylmethyl)estra-1,3,5(10)-triene-3,17β-diol) with an IC50 value of 0.34 μM was found to be more active against the hormone-dependent breast cancer cell line MCF-7 than doxorubicin. These results suggest that a -ring substitution of steroidal estrogens is a plausible strategy for preparing other ferrocene–steroid conjugates acting against tumor cells. 相似文献
42.
Berta Holló Marko V. Rodić Oskar Bera Mirjana Jovičić Vukadin M. Leovac Zoran D. Tomić Katalin Mészáros Szécsényi 《Structural chemistry》2013,24(6):2193-2201
The crystal and molecular structure of [Cu(ampf)(ClO4)(MeOH)2]ClO4, (1), ampf = N,N′-bis(4-acetyl-5-methylpyrazol-3-yl)formamidine, determined by X-ray crystallography is described and compared with the structurally related copper(II) complexes, formed under similar experimental conditions, using CuII salts with different anions. The complex formation is discussed in view of the structures of cobalt(II) and nickel(II) complexes with the same organic ligand and different anions, also formed under similar reaction conditions. Solvent molecules coordinated to the central atom play an important role in biologic systems. To get a better insight into the desolvation mechanism, in this study the desolvation pattern of 1 is presented. As in literature little attention is paid to the desolvation mechanism of solvate complexes, the desolvation mechanism of three, potentially biologically active isostructural pairs of octahedral NiII and CoII compounds with ampf and dmpc (3,5-dimethyl-1H-pyrazole-1-carboxamidine) ligands are evaluated and compared with the desolvation of 1. The results of the thermal data are discussed on the basis of structural features of the compounds. The minor differences in structures of the related compounds cannot be straightforwardly connected with the different solvent evaporation mechanism. To explain the differences found in desolvation pattern in isostructural CoII and NiII complexes the Jahn-Teller effect is proposed. 相似文献
43.
Extensive velocity measurements have been taken in a linear turbine cascade with unsteady oncoming wakes. The unsteady wakes
were generated by moving cylinders on a squirrel cage device. The Reynolds number was 1.1 × 105, and the Strouhal number varied from o to 7.36. The blade-to-blade flow and the boundary layers on the suction side were
measured with a hot-wire anemometer. The results were obtained in ensemble-averaged form so that periodic unsteady processes
can be studied. Of particular interest was the transition of the boundary layer. The boundary layer remained laminar in the
case without wakes. The passing wakes caused transition, and the beginning of transition moves forward as the wake-passing
frequency increases. Unlike in the flat plate study of Liu and Rodi (1991a) the boundary layer state hardly changed with time,
although the turbulence level in the boundary layer showed clear periodic response to the passing wakes.
The work reported here was sponsored by the German Federal Ministry of Research and Technology through program TURBOTHERM
under contract no. 0326501D. The authors should like to thank Mr. D. Bierwirth for his excellent technician work on this project,
Dr. N. H. Cho for his help with the preparation of the plots and Mrs. R. Zschernitz for her expert typing of the text. 相似文献
44.
We have studied the hyperfine interactions in GdIG in zero external magnetic field using57Fe Mössbauer spectroscopy. Measurements were made at temperatures between 80 K and 310 K, whereby the region around the compensation point at 286 K was emphasized. The easy axis of magnetization was determined to be [111] at all the chosen temperatures. No indications of spin canting were found. The hyperfine parameters vary smoothly with temperature. The temperature dependences of the magnetization of the sublattices are deduced from the magnetic hyperfine fields. 相似文献
45.
46.
47.
Rodi DJ Agoston GE Manon R Lapcevich R Green SJ Makowski L 《Combinatorial chemistry & high throughput screening》2001,4(7):553-572
Affinity selection of peptides displayed on phage particles was used as the basis for mapping molecular contacts between small molecule ligands and their protein targets. Analysis of the crystal structures of complexes between proteins and small molecule ligands revealed that virtually all ligands of molecular weight 300 Da or greater have a continuous binding epitope of 5 residues or more. This observation led to the development of a technique for binding site identification which involves statistical analysis of an affinity-selected set of peptides obtained by screening of libraries of random, phage-displayed peptides against small molecules attached to solid surfaces. A random sample of the selected peptides is sequenced and used as input for a similarity scanning program which calculates cumulative similarity scores along the length of the putative receptor. Regions of the protein sequence exhibiting the highest similarity with the selected peptides proved to have a high probability of being involved in ligand binding. This technique has been employed successfully to map the contact residues in multiple known targets of the anticancer drugs paclitaxel (Taxol), docetaxel (Taxotere) and 2-methoxyestradiol and the glycosaminoglycan hyaluronan, and to identify a novel paclitaxel receptor [1]. These data corroborate the observation that the binding properties of peptides displayed on the surface of phage particles can mimic the binding properties of peptides in naturally occurring proteins. It follows directly that structural context is relatively unimportant for determining the binding properties of these disordered peptides. This technique represents a novel, rapid, high resolution method for identifying potential ligand binding sites in the absence of three-dimensional information and has the potential to greatly enhance the speed of development of novel small molecule pharmaceuticals. 相似文献
48.
Guillamón I Suderow H Vieira S Cario L Diener P Rodière P 《Physical review letters》2008,101(16):166407
Scanning tunneling microscopy and spectroscopy measurements in the superconducting dichalcogenide 2H-NbS2 show a peculiar superconducting density of states with two well-defined features at 0.97 and 0.53 meV, located, respectively, above and below the value for the superconducting gap expected from the single band s-wave BCS model (Delta=1.76k_(B)T_(c)=0.9 meV). Both features have a continuous temperature evolution and disappear at T_(c)=5.7 K. Moreover, we observe the hexagonal vortex lattice with radially symmetric vortices and a well-developed localized state at the vortex cores. The sixfold star shape characteristic of the vortex lattice of the compound 2H-NbSe2 is, together with the charge density wave order, absent in 2H-NbS2. 相似文献
49.
A fully vectorised, basically three-dimensional finite-volume multi-block method for flows with complex boundaries is applied in a stripped-down two-dimensional version for the investigation of the flow field in the leading-edge region of a high-pressure turbine blade with slot cooling-jet injection. The calculation results are compared with experiments and the numerical results of other investigators. The present method yields excellent agreement with the experiments for the isentropic Mach number distributions on the blade surface. All numerical results for the velocity field were found to be in very good agreement with each other and with experiments on the suction side, while the agreement is not as good on the pressure side. 相似文献
50.
A Direct Numerical Simulation (DNS) of flow in the V103 Low-Pressure (LP) compressor cascade with incoming wakes was performed.
The computational geometry was chosen largely in accordance with the setup of the experiments performed by Hilgenfeld and
Pfitzner (J Turbomach 126:493–500, 2004) at the University of the Armed Forces in Munich. The computations were carried out on the NEC-SX8 in Stuttgart using 64
processors and 85 million grid points. The incoming wakes stemmed from a separate DNS of incompressible flow around a circular
cylinder with a Reynolds number of Re
d
= 3300 (based on mean inflow velocity and cylinder diameter). The boundary layer along the suction surface of the blade was
found to separate and roll up due to a Kelvin–Helmholtz instability triggered by the periodically passing wakes. Inside the
rolls further transition to turbulence was found to occur. The boundary-layer flow along the pressure surface did not separate,
instead it underwent by-pass transition. 相似文献