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31.
Oleg V. Mikhailov Marina A. Kazymova Tatyana A. Shumilova Galina A. Chmutova Svetlana E. Solovieva 《Transition Metal Chemistry》2005,30(3):299-304
The complexing process proceeding in the NiII–thiocarbohydrazide (H2N–H–NC(=S)–NH–NH2)–propanone triple system in EtOH solution and nickel(II)hexacyanoferrate(II) gelatin-immobilized matrix has been studied. It has been found that in the first case, template synthesis leading, as a minimum, to formation of three coordination compounds of NiII with (N,N,S,S)-donor tetradentate ligands having NiL1, NiL2 and NiL3compositions where L1 is 4,6,6-trimethyl-2,3,7,8-tetraazanonen-3-di(thiohydrazide)-1,9, L2 is 4,6,6,12-tetrametyl-1,9-dithio-2,3,7,8,10,11-hexaazatridekadien-3,11-hydrazide-1 and L3 is 2,8,10,10,16-pentamethyl-5,13-dithio-3,4,6,7,11,12,14,15-octaazaheptadekatrien-2,7,15 is observed, whereas in the gelatin-immobilized matrix, a complexing process in the system considered does not occur. 相似文献
32.
Oleg N. Obrezkov Andrey V. Pirogov Igor V. Pletnev Oleg A. Shpigun 《Mikrochimica acta》1991,103(5-6):293-302
A new optimization criterion for chromatography is presented. It was designed to evaluate the quality of chromatograms in a way similar to human estimation. Selectivity, efficiency, and time of analysis as well as the number of peaks were taken into account. The criterion has been tested in comparison with expert estimations and some modern criteria. A better agreement of the new criterion with human estimation of chromatographic quality compared to some literature criteria is shown. A number of successful optimization runs has been performed using the criterion together with simplex optimization. 相似文献
33.
Kostko O Wrigge G Cheshnovsky O von Issendorff B 《The Journal of chemical physics》2005,123(22):221102
We present photoelectron spectroscopy studies on Zn(n) (-) in the size range of n=3-117. We show that zinc clusters exhibit a distinct transition in their electronic structure as a function of size. At small sizes (up to n=18) the clusters follow the Bloch-Wilson picture of the development of a metal from closed-shell atoms, exhibiting a gradual decrease of the gap between the fully occupied s band and the empty p band. For large sizes (n approximately or > 32) the band overlap allows the valence electrons to fully delocalize. This leads to an almost perfect free-electron density of states, as is demonstrated by discussing the spectra in the light of standard free-electron models and by comparison to the results obtained on sodium clusters. 相似文献
34.
Constant magnetic fields affect many biological transformations, but we lack mechanistic understanding of the processes. The magnetohydrodynamic effect may account for the enhancement of bioelectrocatalytic transformations at interfaces. This is exemplified by the bioelectrocatalyzed cytochrome c-mediated reduction of oxygen and oxidation of lactate in the presence of cytochrome oxidase and lactate dehydrogenase, respectively. We observe significant magnetic field effects on the rates of bioelectrochemical transformations (ca. 3-fold increase) at the functionalized interfaces at field strengths, B, up to 1 T. We show that the limiting current is proportional to the B(1/3)C*(4/3), where C is the concentration of electroactive species. The results may have important implications on the understanding of the magnetic field effects on natural biocatalytic processes at membranes and on the enhancement of biotransformations in biotechnology. 相似文献
35.
This report examines reactions of a series of Ir complexes supported by the diarylboryl/bis(phosphine) PBP pincer ligand with ethylene: (PBP)IrH4 (1), (PBP)IrH2(CO) (2), and (PBP)Ir(CO)2 (3). The outcomes of these reactions differ from those typical for Ir complexes supported by other pincer ligands and do not give rise to simple ethylene adducts or products of insertion of Ir into the C–H bond of ethylene. Instead, the elements of ethylene are incorporated into the molecules to result in B–C bonds. In the case of 2 and 3, ethylene addition results in the formation of B/Ir bridging ethylidene complexes 5 and 6. For 6, the addition of ethylene (and the analogous addition of 1-hexene) is shown to be partially reversible. Addition of ethylene to 2 and 3 is remarkable because they are saturated at Ir and yet the net outcome is such that ethylene binds without replacing any ligands already present. A mechanistic inquiry suggests that dissociation of CO from 3 or 6 is necessary in order for the addition or loss of ethylene to proceed.(PBP)Ir pincer complexes containing a boryl-iridium linkage reversibly bind ethylene as an ethylidene bridging B and Ir. 相似文献
36.
Amelichev SA Aysin RR Konstantinova LS Obruchnikova NV Rakitin OA Rees CW 《Organic letters》2005,7(25):5725-5727
[chemical reaction: see text]. Treatment of N-substituted 2,5-dimethylpyrroles 2 with an equilibrated mixture of disulfur dichloride and DABCO in chloroform at 0 degrees C gives pentathiepinopyrroles 3 in moderate yields; further reaction of 3 with the same mixture at room temperature leads, in an extensive reaction cascade, to bis(dithiolo)pyrroles 4 in high yield; 2 can be converted into 4 in a one-pot operation under unusually mild conditions. 相似文献
37.
A superoxochromium(III) ion, CraqOO2+, acts as a catalyst for the co-oxidation of alcohols and nitrous acid with molecular oxygen according to the stoichiometry: CH3OH+HNO2+O2→CH2O + NO3− + H2O+H+. The kinetics are second order in [HNO2] and independent of the concentrations of the superoxochromium catalyst, substrate, and O2. The proposed mechanism features the disproportionation of HNO2 to NO and NO2, both of which react rapidly with CraqOO2+. The CraqOO2+/NO reaction generates another equivalent of NO2 and a mole of CraqO2+, the active oxidant. The two-electron oxidation of the alcohol by CraqO2+ produces Craq2+, which reacts rapidly with O2 to regenerate the catalyst, CraqOO2+. The NO2/CraqOO2+ reaction yields the peroxynitrato complex, CraqOONO22+, in a dead-end equilibrium process that has no effect on the catalytic reaction. The disproportionation of NO2 yields the final nitrogen-containing product, NO3−, and regenerates an equivalent of HNO2. Under a fixed set of conditions, the relative catalytic efficiency (CE) of CraqOO2+ decreases as its concentration increases owing to the competition between O2 and CraqOO2+ for the intermediate Craq2+. 相似文献
38.
Lukin O Müller WM Müller U Kaufmann A Schmidt C Leszczynski J Vögtle F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(15):3507-3517
The readily available in gram quantities tris(allyloxy)knot of the amide-type 5 (knotane) can be completely and partially deprotected with nBu(3)SnH in the presence of a palladium catalyst resulting in hydroxyknotanes 7-9. These, in turn, react with diethylchlorophosphate giving rise to knotanes equipped with between one and three phosphoryl groups. Sulfonylation of bis(allyloxy)monohydroxyknotane 8 with p-toluenesulfonyl chloride and, following removal of one or two allyl groups from the intermediate monosulfonate 13, give rise to sulfonyloxy-allyloxy-hydroxy- and sulfonyloxy-dihydroxy-knotanes 15 and 14, respectively. This provides a convenient method for the preparation of knotanes with any substitution pattern. All new knotanes have been isolated in preparative amounts and as highly pure substances with an exception of allyloxy-dihydroxyknotane 9. This compound could only be obtained as a mixture with the corresponding monohydroxy-derivative 8. The structures of all synthesized compounds were established by means of FAB and MALDI TOF mass spectrometry, (1)H and (31)P NMR spectroscopy. The triphosphorylated knotane 10 exhibits high solubility in alcohols, allowing its complete enantiomeric resolution with a commercially available chiral HPLC column. (1)H,(1)H DQF-COSY correlation spectroscopy along with H/D exchange experiments and ab initio calculations provided the first detailed (1)H NMR signal assignments of knotanes in [D(6)]DMSO solution. The combination of variable temperature (1)H and (31)P NMR spectroscopy and molecular modeling has been applied to study the conformational behavior of the new knotanes in different solvents. It has been shown that in DMSO solution at room temperature knotanes exist in a relatively rigid nonsymmetrical conformation similar to that found in the solid state while faster conformational exchange leading to the average D(3) symmetrical structure was detected in a number of other solvents. 相似文献
39.
Rueda D Boyarkin OV Rizzo TR Chirokolava A Perry DS 《The Journal of chemical physics》2005,122(4):44314
Spectra of jet-cooled methanol in the overtone and combination region from 5000 to 14 000 cm(-1) have been obtained by means of infrared laser-assisted photofragment spectroscopy. Many of the observed features are assigned to combination bands of the type nnu(1)+nu(6), nnu(1)+nu(8), and nnu(1)+nu(6)+nu(8) (n=1,2,3), where nu(1) is the OH stretch, nu(6) is the OH bend, and nu(8) is the CO stretch. These bands show sharp torsion-rotation structure with features as narrow as 0.1 cm(-1). We also observe CH stretch overtones that are weaker than the OH containing combination bands and lack distinct torsion-rotation structure above v(CH)=2. The extent of observed structure on these bands allows us to place limits on the intramolecular vibrational energy redistribution decay rates in the upper vibrational states. We report a global fit of the observed band centers to a simple expression involving low-order anharmonicity constants. 相似文献
40.
Antzutkin ON 《Magnetic resonance in chemistry : MRC》2004,42(2):231-246
Aggregation cascade for Alzheimer's amyloid-beta peptides, its relevance to neurotoxicity in the course of Alzheimer's disease and experimental methods useful for these studies are discussed. Details of the solid-phase peptide synthesis and sample preparation procedures for Alzheimer's beta-amyloid fibrils are given. Recent progress in obtaining structural constraints on Abeta-fibrils from solid-state NMR and scanning transmission electron microscopy (STEM) data is discussed. Polymorphism of amyloid fibrils and oligomers of the 'Arctic' mutant of Abeta(1-40) was studied by (1)H,(13)C solid-state NMR, transmission electron microscopy (TEM) and atomic force microscopy (AFM), and a real-time aggregation of different polymorphs of the peptide was observed with the aid of in situ AFM. Recent results on binding of Cu(II) ions and Al-citrate and Al-ATP complexes to amyloid fibrils, as studied by electron paramagnetic resonance (EPR) and solid-state (27)Al NMR techniques, are also presented. 相似文献