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51.
The reactions of Cu(ClO4)2·6H2O with 6-(benzylamino)purine derivatives in a stoichiometric 1:2 metal-to-ligand ratio led to the formation of penta-coordinated dinuclear complexes of the formula [Cu2(μ-L1–8)4(ClO4)2](ClO4)2·nsolv, where L1 = 6-(2-fluorobenzylamino)purine (complex 1), L2 = 6-(3-fluorobenzylamino)purine (2), L3 = 6-(4-fluorobenzylamino)purine (3), L4 = 6-(2-chlorobenzylamino)purine (4), L5 = 6-(3-chlorobenzylamino)purine (5), L6 = 6-(4-chlorobenzylamino)purine (6), L7 = 6-(3-methoxybenzylamino)purine (7) and L8 = 6-(4-methoxybenzylamino)purine (8); n = 0–4 and solv = H2O, EtOH or MeOH. All the complexes have been fully characterized by elemental analysis, FTIR, UV–Vis and EPR spectroscopy, and by magnetic and conductivity measurements. Variable temperature (80–300 K) magnetic susceptibility data of 1–8 showed the presence of a strong antiferromagnetic exchange interaction between two Cu(II) (S = 1/2) atoms with J ranging from −150.0(1) to −160.3(2) cm−1. The compound 6·4EtOH·H2O was structurally characterized by single crystal X-ray analysis. The Cu?Cu separation has been found to be 2.9092(8) Å. The antiradical activity of the prepared compounds was tested by in vitro SOD-mimic assay with IC50 in the range 8.67–41.45 μM. The results of an in vivo antidiabetic activity assay were inconclusive and the glycaemia in pre-treated animals did not differ significantly from the positive control. 相似文献
52.
Alena Průšová Pellegrino Conte Jiří Kučerík Giuseppe Alonzo 《Analytical and bioanalytical chemistry》2010,397(7):3023-3028
Fast field cycling (FFC) NMR relaxometry has been used to study the conformational properties of aqueous solutions of hyaluronan
(HYA) at three concentrations in the range 10 to 25 mg mL–1. Results revealed that, irrespective of the solution concentration, three different hydration layers surround hyaluronan.
The inner layer consists of water molecules strongly retained in the proximity of the HYA surface. Because of their strong
interactions with HYA, water molecules in this inner hydration layer are subject to very slow dynamics and have the largest
correlation times. The other two hydration layers are made of water molecules which are located progressively further from
the HYA surface. As a result, decreasing correlation times caused by faster molecular motion were measured. The NMRD profiles
obtained by FFC-NMR relaxometry also showed peaks attributable to 1H–14N quadrupole interactions. Changes in intensity and position of the quadrupolar peaks in the NMRD profiles suggested that
with increasing concentration the amido group is progressively involved in the formation of weak and transient intramolecular
water bridging adjacent hyaluronan chains. In this work, FFC-NMR was used for the first time to obtain deeper insight into
HYA–water interactions and proved itself a powerful and promising tool in hyaluronan chemistry. 相似文献
53.
54.
Jan ?ermák Alena Krupková Milan Zamrzla Pavel Vojtíšek 《Journal of organometallic chemistry》2010,695(3):375-381
Tetramethyl(perfluoroalkyl)cyclopentadienyl rhodium(I) complexes with ethylene or diene (norbornadiene, cycloocta-1,5-diene, 2,3-dimethylbuta-1,3-diene, cyclohexa-1,3-diene) ligands were obtained by reduction of tetramethyl(perfluoroalkyl)rhodium(III) dichloro dimers by zinc in THF or by propan-2-ol/sodium carbonate in the presence of the ligands. Reduction in the presence of cycloocta-1,3-diene gave a different product, an η3-cyclooctenyl complex, which was not reduced further. During the reduction in the presence of ethylene, a new tetramethyl(perfluoroalkyl)-η4-cyclopentadiene complex was observed by NMR. This compound, formed by hydrogen transfer from the metal to the ligand, is probably in an equilibrium with the parent hydridocyclopentadienyl complex. Crystal and molecular structure of dicarbonyltetramethyl(perfluorohexyl)cyclopentadienylrhodium(I) complex was determined by X-ray diffraction. The structure shows a moderate ring slippage of the rhodium atom which was not observed in the only other known structure of a complex with the same ligand, the rhodium(III) dichloro dimer. 相似文献
55.
den Hartog T Rudolph A Maciá B Minnaard AJ Feringa BL 《Journal of the American Chemical Society》2010,132(41):14349-14351
Cu-TolBINAP-catalyzed conjugate addition of Grignard reagents to 4-chloro-α,β-unsaturated esters, thioesters, and ketones leads to 4-chloro-3-alkyl-substituted thioesters and ketones in up to 84% yield and up to 96% ee upon protonation of the corresponding enolates at low temperature. Tandem conjugate addition-enolate trapping, however, yields trans-1-alkyl-2-substituted cyclopropanes in up to 92% yield and up to 98% ee. The versatility of this reaction is illustrated by the formation of key intermediates for the formal syntheses of cascarillic acid and grenadamide. 相似文献
56.
Inna P. Tsypysheva Alexander N. Lobov Alena V. Kovalskaya Polina R. Petrova Sergey P. Ivanov Shamil A. Rameev 《Natural product research》2015,29(2):141-148
The first example of aza-Michael reaction of 12-N-carboxamide of quinolizidine alkaloid (–)-cytisine with α,β-unsaturated ketones, dimethyl acetylenedicarboxylate and β-nitrostyrene under high pressure condition has been described. It has been shown that the [4+2]-cycloaddition takes place in the case with N-phenylmaleimide. 相似文献
57.
The spectrochemical behavior of nonvolatile tungsten and boron was tested by adding different buffers and using 12 A ac arc excitation. The oxidization and sulfidization processes were found to be most effective for facilitating the volatilization. The optimal admixture was the copper oxide buffer for both the detection limit and the precision of the method. The reference values of the background or a palladium line blackening were used. 相似文献
58.
Victor Burakov Vasilii Kiris Alena Klyachkovskaya Natalia Kozhukh Sergei Raikov 《Mikrochimica acta》2006,156(3-4):337-342
Laser-induced breakdown spectroscopy has been applied to layer-by-layer pigment material microanalysis from the different
sections of Hubert Robert’s (1733–1808) painting “Landscape of a Pool with an Obelisk and Ruins of an Aqueduct”. This painting
consists of two sections and, therefore, requires thorough examination of the pigments from both sections in order to identify
their authenticity. The data obtained on the elemental composition of the paint layers including the ground layer alongside
with art examination have formed the basis for the identification, attribution and restoration of both investigated sections
of the painting. 相似文献
59.
The history, origin, and development of a system for monitoring and assessing water and other environmental laboratories in
the Czech Republic is described. The system started in 1991 and has matured to its present complexity with similarities to
the accreditation systems found in other countries. Differences from internationally recognized procedures are being corrected
step by step. During the first year of its existence ASLAB, as part of its brief, organised proficiency testing (PT) programs
for fifty laboratories. Today the total number of regularly participating laboratories exceeds 700 from the Czech Republic,
the Slovak Republic, and Germany. This paper describes the ASLAB PT system, discusses some experiences with its use, and describes
the use of PT results in assessment of the competence of laboratories.
Received: 12 October 2000 Accepted: 7 January 2001 相似文献
60.