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71.
Dalibor Merunka 《Solid State Communications》2004,129(6):375-377
The modified strong dipole-proton coupling (MSDPC) model, which predicted several static and dynamic dielectric properties of KH2PO4 or KDP-type ferroelectrics, was used to investigate the properties of these crystals on the local scale. Results calculated by molecular dynamics (MD) simulation show that both order-disorder and displacive characteristics of one PO4 dipole are present in KDP and KD2PO4 (DKDP). These results correlate with experimental data from NMR and neutron scattering studies of local properties. 相似文献
72.
Ar-Rh(III) pivalate complexes assembled in situ from the reaction of [RhCl(coe)2]2 (coe = cis-cyclooctene), [p-(CF3)C6H4]3P, and CsOPiv effectively catalyzed the direct C-arylation of free (NH)-indoles and (NH)-pyrroles in good yields and with high regioselectivity. The reaction displayed excellent functional group compatibility and low moisture sensitivity. Kinetics studies support a mechanism involving phosphine displacement by indole in complex 2 (resting state of the catalyst), followed by a rate-limiting C-H bond metalation. 相似文献
73.
The development of a new chemical transformation, namely oxidative C-arylation of saturated (NH)-heterocycles, is described. This reaction combines dehydrogenation and arylation in one process, leading to cross-coupling of (NH)-heterocycles and haloarenes. Typical reaction conditions involve heating the reaction partners in anhydrous dioxane at 120-150 degrees C in the presence of RhCl(CO)[P(Fur)3]2 as the catalyst and Cs2CO3 as the base. Addition of tert-butylethylene as the hydrogen acceptor increases the chemical yield by diminishing the dehalogenation pathway. This method demonstrated a good substrate scope, allowing for cross-coupling of a variety of (NH)-heterocycles (e.g., pyrrolidine, piperidine, piperazine, morpholine) and halo(hetero)arenes to afford valuable heterocyclic products in one step. The preliminary mechanistic studies provided some insight regarding the key events in the proposed catalytic cycle, including beta-hydride elimination of an amido rhodium complex and carbometalation of the resulting imine. A large kinetic isotope effect [KIE (kC-H/kC-D) = 4.3] suggests that one or both beta-hydride elimination steps are rate determining. The central role for the phosphine ligand was established in controlling the partitioning between the oxidative C-arylation and N-arylation pathways. 相似文献
74.
We establish an invariance principle for a general class of stationary random fields indexed by Zd, under Hannan’s condition generalized to Zd. To do so we first establish a uniform integrability result for stationary orthomartingales, and second we establish a coboundary decomposition for certain stationary random fields. At last, we obtain an invariance principle by developing an orthomartingale approximation. Our invariance principle improves known results in the literature, and particularly we require only finite second moment. 相似文献
75.
Jan Tborský Josef Sus Jaromír Lachman Barbora ebkov Aneka Adamcov Dalibor atínský 《Molecules (Basel, Switzerland)》2021,26(13)
Apple trees (Malus domestica Borgh) are a rich source of dihydrochalcones, phenolic acids and flavonoids. Considering the increasing demand for these phytochemicals with health-benefitting properties, the objective of this study was to evaluate the profile of the main bioactive compounds—phloridzin, phloretin, chlorogenic acid and rutin—in apple tree bark, leaves, flower buds and twigs. The variety in the phenolic profiles of four apple tree cultivars was monitored during the vegetation period from March to September using chromatography analysis. Phloridzin, the major glycoside of interest, reached the highest values in the bark of all the tested cultivars in May (up to 91.7 ± 4.4 mg g−1 of the dried weight (DW), cv. ‘Opal’). In the leaves, the highest levels of phloridzin were found in cv. ‘Opal’ in May (82.5 ± 22.0 mg g−1 of DW); in twigs, the highest levels were found in cv. ‘Rozela’ in September (52.4 ± 12.1 mg g−1 of DW). In the flower buds, the content of phloridzin was similar to that in the twigs. Aglycone phloretin was found only in the leaves in relatively low concentrations (max. value 2.8 ± 1.4 mg g−1 of DW). The highest values of rutin were found in the leaves of all the tested cultivars (10.5 ± 2.9 mg g−1 of DW, cv. ‘Opal’ in September); the concentrations in the bark and twigs were much lower. The highest content of chlorogenic acid was found in flower buds (3.3 ± 1.0 mg g−1 of DW, cv. ‘Rozela’). Whole apple fruits harvested in September were rich in chlorogenic acid and phloridzin. The statistical evaluation by Scheffe’s test confirmed the significant difference of cv. ‘Rozela’ from the other tested cultivars. In conclusion, apple tree bark, twigs, and leaves were found to be important renewable resources of bioactive phenolics, especially phloridzin and rutin. The simple availability of waste plant material can therefore be used as a rich source of phenolic compounds for cosmetics, nutraceuticals, and food supplement preparation. 相似文献
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78.
Yttrium aluminum garnet and perovskite activated by cerium are fast mechanically and chemically resistant scintillation materials. Their mechanical properties enable easy and precise machining. Both scintillation materials have a decay time shorter than 100 ns and, therefore, are suitable to use for high counting rates. The luminescence maximum of YAP:Ce and YAG:Ce are 360 and 550 nm, respectively. Their luminescence bands correspond with the sensitivity spectral range of the most widely used photomultipliers. Moreover, the semiconductor light detectors can be used with YAG:Ce scintillation crystals. Theoretical and experimental comparative analysis of characteristics for both YAP:Ce and YAG:Ce detectors and good experience over relatively long periods of using these detectors allow us to draw a conclusion regarding their unconditional advantages over other commonly used detectors for transmission Mössbauer spectroscopy. The considerable improvement in data production enhances the capabilities of Mössbauer spectroscopy as a research and analytical tool. 相似文献
79.
Petr Chocholouš Dalibor Šatínský Radek Sladkovský Marie Pospíšilová Petr Solich 《Talanta》2008,77(2):566-570
Sequential injection chromatography system equipped with miniaturized 10 mm monolithic column was used for fast simultaneous determination of two pesticides—fenoxycarb (FC) and permethrin (PM). The system was composed of a commercial sequential injection analysis (SIA) system (FIAlab® 3000, 6-port selection valve and 5.0 mL syringe pump), commercially available column Chromolith™ RP-18e (10 mm × 4.6 mm i.d.) (Merck®, Germany) and CCD UV-vis detector (USB 2000, Ocean-optics) with 1.0 cm Z-flow cell, absorbance was monitored at 225 nm. The mobile phase used for analysis was acetonitrile/water (60:40, v/v), flow rates were 0.6 mL min−1 for elution of fenoxycarb and 1.2 mL min−1 for elution of permethrin. For each analysis 4.8 mL of mobile phase was used. The chromatographic resolution between both compounds was >8 and analysis time was <6.5 min under the optimal conditions. Limits of detection were determined at 2.0 μg mL−1 for fenoxycarb and 1.0 μg mL−1 for permethrin. Samples were prepared by diluting with mobile phase and injected volume was 10 μL for each analysis. Developed method was applied to analysis of both pesticides in veterinary pharmaceutical foams and sprays ARPALIT® Neo (Aveflor, Czech Republic). SIC method was compared with validated method (HPLC, reverse phase 100 mm monolithic column, gradient elution). 相似文献
80.
We have developed a luminogenic probe for tyrosine phosphorylation based on a short peptide sequence containing an iminodiacetate moiety near the site of phosphorylation. In response to kinase activity, the probe provides a strong luminescence enhancement, resulting from the increased ability of the probe to bind and sensitize Tb3+ and Eu3+ ions upon phosphorylation. 相似文献