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21.
Emanuel Knill 《Graphs and Combinatorics》1994,10(2-4):145-157
A family of sets ? islocally k- wide if and only if the width (as a poset ordered by inclusion) of ? is at mostk for everyx. The directed covering graph of a locally 1-wide family of sets is a forest of rooted trees. It is shown that if ? is a locallyk-wide family of subsets of {1,...,n}, then |?|≤(2k) k?1 n. The proof involves a counting argument based on families of closed sets associated with theSperner closures in the filters of ?. The Sperner closure ofU in ? is the intersection of the members of the greatest Sperner antichain of ? U = {V ∈ ?|V ?U}. This closure operation is related to a generalization of maximality in posets. 相似文献
22.
Sille Ehala Rajendra Rathore Emanuel Makrlík Petr Toman Václav Kašička 《Procedia Chemistry》2010,2(1):14-19
Affinity capillary electrophoretic (ACE) study has proved the selectivity of hexaarylbenzene-based polyaromatic receptor (R) for K+ ion over Na+ ion. The apparent binding constants of the R complexes with K+ and Na+ ions were determined from the dependence of effective electrophoretic mobility of R on the concentration of the above alkali metal ions in the background electrolyte using a non-linear regression analysis. The apparent binding constants (Kb) of the K-R+ and Na–R+ complexes in methanolic medium were evaluated as log Kb = 3.20 ± 0.22 for the K–R+ complex, and log Kb??0.7 for the Na–R+ complex. 相似文献
23.
Ji?í Dybal Emanuel Makrlík Jan Budka Petr Vaňura 《Monatshefte für Chemie / Chemical Monthly》2008,275(2):1353-1355
Using DFT calculations, two of the most probable structures (A, B) of the tetraphenyl p-tert-butylcalix[4]arene tetraketone·H3O+ cationic complex species were derived. The hydroxonium ion H3O+, placed in the coordination cavity formed by the calix[4]arene lower-rim groups, is bound by strong hydrogen bonds to the
phenoxy oxygen atoms of the calix[4]arene ligand (structures A, B) and also to one carbonyl oxygen (structure B). 相似文献
24.
Klejdus B Lojková L Kula E Buchta I Hrdlicka P Kubán V 《Journal of separation science》2008,31(8):1363-1373
A method for supercritical fluid extraction (SFE) of amino acids was adapted and optimal experimental conditions were selected for a matrix consisting of dry leaves. The matrix-dependent SFE method uses a mixture of MeOH-H(2)O-acetonitrile (10:10:1 v/v/v) as a modifier (0.5 mL in situ, 300 muL on-line) at 70 degrees C and 40 MPa and no HCl is needed as an entrainer. The amino acids were quantified using high-performance liquid chromatography with fluorimetric detection (HPLC/FLD) after gradient elution on Zorbax Eclipse AAA columns (4.6x150 mm, 3.5 mum) with aqueous Na(2)HPO(4 )buffer of pH 7.8 and ACN-MeOH-water as a mobile phase. In comparison with Soxhlet extraction, SFE gave higher recovery and selectivity, but it required longer extraction time (90 min) and it was more labor-intensive (clean-up step after the pre-concentration). Both methods should be used separately or in combination according to the matrix, number of samples, and levels of ballast compounds. 相似文献
25.
Emanuel Šucman Miroslava Mahrová Jiří Páč Milada Vávrová Peter Kettisch 《Electroanalysis》2008,20(4):386-389
Anodic stripping voltammetry is useful instrumental method for trace element determination in biological materials. It is however extremely demanding to the quality of the sample preparation process. The high‐pressure microwave assisted digestion seems to meet its requirements. The differential pulse anodic stripping voltammetry technique was used for determination of cadmium, copper, lead and zinc in certified reference materials both of plant and of animal origin to prove the analytical properties of such sample preparation method. The found concentrations have been in satisfactory agreement with the certified values. The elaborated digestion procedure is greatly universal and has required accuracy and precision. 相似文献
26.
N. M. Emanuel Z. K. Maizus V. G. Vinogradova 《Reaction Kinetics and Catalysis Letters》1981,17(1-2):77-82
The dependence of inhibiting properties of M(dtc) on M for the complexes of M(II) and n M(III) has been studied. Inhibition is due to the interaction of M(dtc)n with RO2.
M(dtc)n M M(II) M(III). M(dtc)n RO2.相似文献
27.
ACE was applied to the quantitative evaluation of noncovalent binding interactions between benzo‐18‐crown‐6‐ether (B18C6) and several alkali metal ions, Li+, Na+, K+, Rb+ and Cs+, in a mixed binary solvent system, methanol–water (50/50 v/v). The apparent binding (stability) constants (Kb) of B18C6–alkali metal ion complexes in the hydro‐organic medium above were determined from the dependence of the effective electrophoretic mobility of B18C6 on the concentration of alkali metal ions in the BGE using a nonlinear regression analysis. Before regression analysis, the mobilities measured by ACE at ambient temperature and variable ionic strength of the BGE were corrected by a new procedure to the reference temperature, 25°C, and the constant ionic strength, 10 mM . In the 50% v/v methanol–water solvent system, like in pure methanol, B18C6 formed the strongest complex with potassium ion (log Kb=2.89±0.17), the weakest complex with cesium ion (log Kb=2.04±0.20), and no complexation was observed between B18C6 and the lithium ion. In the mixed methanol–water solvent system, the binding constants of the complexes above were found to be about two orders lower than in methanol and about one order higher than in water. 相似文献
28.
29.
Colnaghi Simionato AV da Silva DS Lambais MR Carrilho E 《Journal of mass spectrometry : JMS》2007,42(4):490-496
Xylella fastidiosa (X.f.) is a plant pathogen with high levels of genomic similarity to Xanthomonas campestris pv. campestris (X.c.c.). It has been shown that X. fastidiosa synthesizes a putative diffusible signal factor (X.f.-DSF) that activates regulation of pathogenicity factor (rpf) genes in a X.c.c. reporter system, which might be involved in the regulation of pathogenesis associated genes as in X.c.c., as well as in quorum-sensing. The nature of the X.f.-DSF is not known, whereas the X.c.c.-DSF has been identified as cis-11-methyl-2-dodecenoic acid. In this work, the chemical nature of a putative X.f.-DSF molecule, able to restore endoglucanase activity in a X.c.c. rpfF mutant, was investigated as if it was a fatty acid derivative. Bioassays with X.c.c. reporter bacterium and X.f. culture extracts, based on endoglucanase restoration activity, were also carried out in order to confirm the DSFs molecules similarities. For this reason, a gas chromatography-mass spectrometry method was developed with standard fatty acids methyl esters mixtures. The retention time, as well as the fragmentation patterns, of each standard was used to identify the DSF molecule synthesized by X.f. in the culture medium. Typical ester fragmentation patterns (the derivatized analyte) were observed, such as: McLafferty rearrangement and migration of the Hdelta followed by 1,4-hydrogen shift and cleavage of the bond Cbeta-Cgamma, confirming the nature of this molecule. This confirmation was corroborated by the common peaks in both spectra. Besides, the observed retention time reinforces our conclusion since it corresponds to a methyl ester with 15 carbons. Since the X.f.-DSF molecule was tentatively identified as 12-methyl-tetradecanoic acid (by mass spectra library comparison), this standard compound was also analyzed, strongly suggesting that this is the identification of such a molecule. To our knowledge, this is the first time a DSF produced by X.f. has been characterized. 相似文献
30.
McKeown BA Gonzalez HE Friedfeld MR Gunnoe TB Cundari TR Sabat M 《Journal of the American Chemical Society》2011,133(47):19131-19152
Cationic platinum(II) complexes [((t)bpy)Pt(Ph)(L)](+) [(t)bpy =4,4'-di-tert-butyl-2,2'-bipyridyl; L = THF, NC(5)F(5), or NCMe] catalyze the hydrophenylation of ethylene to generate ethylbenzene and isomers of diethylbenzene. Using ethylene as the limiting reagent, an 89% yield of alkyl arene products is achieved after 4 h at 120 °C. Catalyst efficiency for ethylene hydrophenylation is diminished only slightly under aerobic conditions. Mechanistic studies support a reaction pathway that involves ethylene coordination to Pt(II), insertion of ethylene into the Pt-phenyl bond, and subsequent metal-mediated benzene C-H activation. Studies of stoichiometric benzene (C(6)H(6) or C(6)D(6)) C-H/C-D activation by [((t)bpy)Pt(Ph-d(n))(THF)](+) (n = 0 or 5) indicate a k(H)/k(D) = 1.4(1), while comparative rates of ethylene hydrophenylation using C(6)H(6) and C(6)D(6) reveal k(H)/k(D) = 1.8(4) for the overall catalytic reaction. DFT calculations suggest that the transition state for benzene C-H activation is the highest energy species along the catalytic cycle. In CD(2)Cl(2), [((t)bpy)Pt(Ph)(THF)][BAr'(4)] [Ar' = 3,5-bis(trifluoromethyl)phenyl] reacts with ethylene to generate [((t)bpy)Pt(CH(2)CH(2)Ph)(η(2)-C(2)H(4))][BAr'(4)] with k(obs) = 1.05(4) × 10(-3) s(-1) (23 °C, [C(2)H(4)] = 0.10(1) M). In the catalytic hydrophenylation of ethylene, substantial amounts of diethylbenzenes are produced, and experimental studies suggest that the selectivity for the monoalkylated arene is diminished due to a second aromatic C-H activation competing with ethylbenzene dissociation. 相似文献