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111.
Izabela Kaminska Joanna Niedziolka-Jonsson Agata Roguska Marcin Opallo 《Electrochemistry communications》2010,12(12):1742-1745
Gold nanoparticles have been electrodeposited on an electrode through electrogeneration at an ITO|AuCl4? solution in an ionic liquid|aqueous electrolyte three-phase junction. The electrodeposition was carried out by inverted double-pulse potential chronoamperometry. The direct reduction of AuCl4? ions at the electrode is followed by a counterion transfer through the liquid|liquid interface. Contrary to the electrodeposition from a single ionic liquid phase, scanning electron microscopy reveals that the shape of the resulting nanoparticles is highly angular and well-developed with a diameter of 110 ± 30 nm. Catalytic oxidation of glucose on the modified electrode is demonstrated. 相似文献
112.
Katarzyna Szot John D. Watkins Steven D. Bull Frank Marken Marcin Opallo 《Electrochemistry communications》2010,12(6):737-739
Three dimensional carbon film electrodes were prepared from oppositely charged carbon nanoparticles (ca. 9 to 18 nm diameter) by a layer-by-layer approach. This was done by alternative immersion of indium tin oxide plates into suspension of positively and negatively charged particles. A stable film is formed already after single immersion and withdrawal step as confirmed by scanning electron microscopy. Up to ten immersion and withdrawal steps can be used to systematically increase the amount of nanoparticulate carbon material. The capacitive current density and current density of hydrogen peroxide reduction are proportional to the number of immersion and withdrawal steps. The same can be seen for adsorbed redox active 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate). After adsorption of bilirubin oxidase into the film efficient bioelectrocatalytic dioxygen reduction is observed. 相似文献
113.
The absolute configurations of 2-cyclohexenone cis-diol metabolites resulting from the biotransformation of the corresponding phenols have been determined by comparison of their experimental and calculated circular dichroism spectra (TDDFT at the PCM/B2LYP/Aug-cc-pVTZ level), optical rotations (calculated at the PCM/B3LYP/Aug-cc-pVTZ level) and by stereochemical correlation. It is found that circular dichroism spectra and optical rotations of 2-cyclohexenone derivatives are strongly dependent on the ring conformation (M or P sofa S(5) or half-chair), enone non-planarity and the nature and positions of the hydroxy and alkyl substituents. The effect of non-planarity of the enone chromophore, including the distortion of the C=C bond, is determined for the model structures by TDDFT calculations at the PCM/B2LYP/6-311++G(2d,2p) level. Non-planarity of the C=C bond in the enone chromophore is commonly encountered in 2-cyclohexenone derivatives and it is a source of significant rotatory strength contribution to the electronic circular dichroism spectra. It is shown that the two lowest-energy transitions in acrolein and 2-cyclohexenone and its derivatives are n(C=O)-π(C=O)* and π(C=C)-π(C=O)*, as expected, while the shorter-wavelength (below 200 nm) transitions are of more complex nature. In 2-cyclohexenone and its alkyl derivatives it is predominantly a mixture of π(C=C)-π(C=C)* and π(C=C)-σ* transitions, whereas the presence of hydroxy substituent results in a dominant contribution due to the n(OH)-π(C=O)* transition. A generalized model for correlation of the CD spectra of 2-cyclohexenones with their structures is presented. 相似文献
114.
The influence of various small- and medium-size basis sets used in Hartree-Fock (HF) and density functional theory (DFT)/B3LYP calculations on results of quantum theory of atoms in molecules based (QTAIM-based) analysis of bond parameters is investigated for several single, double, and triple covalent bonds. It is shown that, in general, HF and DFT/B3LYP methods give very similar QTAIM results with respect to the basis set. The smallest 6-31G basis set and DZ-quality basis sets of Dunning type lead to poor results in comparison to those obtained by the most reliable aug-cc-pVTZ. On the contrary, 6-311++G(2df,2pd) and in a somewhat lesser extent 6-311++G(3df,3pd) basis sets give satisfactory values of QTAIM parameters. It is also demonstrated that QTAIM calculations may be sensitive for the method and basis set in the case of multiple and more polarized bonds. 相似文献
115.
Catalytic ignition of ionic liquids for propellant applications 总被引:1,自引:0,他引:1
Shamshina JL Smiglak M Drab DM Parker TG Dykes HW Di Salvo R Reich AJ Rogers RD 《Chemical communications (Cambridge, England)》2010,46(47):8965-8967
In this proof of concept study, the ionic liquids, 2-hydroxyethylhydrazinium nitrate and 2-hydroxyethylhydrazinium dinitrate, ignited on contact with preheated Shell 405 (iridium supported on alumina) catalyst and energetically decomposed with no additional ignition source, suggesting a possible route to hydrazine replacements. 相似文献
116.
Raquel González de Orduña Mikael Hult Erica Andreotti Dušan Budjáš Stefan Schönert Marcin Misiaszek 《Journal of Radioanalytical and Nuclear Chemistry》2010,286(2):477-482
A simple technique for pulse shape discrimination in HPGe-detectors of the so-called BEGe type, based on just one parameter obtained from one signal read out, is presented here. This technique allows discriminating between pulses generated when the deposited energy is located within a small region of about 1 mm3 from the pulses generated when the energy is deposited at different locations several mm or cm apart. Two possible applications using this technique are: (i) experiments that look for neutrinoless double β decay in 76Ge, such as GERDA; (ii) γ spectrometry measurements where the Compton continuum can be reduced and the efficiency for cascading γ-rays can remain high. With this active background reduction technique a Compton suppression factor of about 3 was obtained. The detector response may be influenced by the detector size. The detector used for this study had a diameter of 6 cm, a thickness of 2.6 cm and a relative efficiency of 19%. The results obtained with this detector were consistent with the results obtained by Budjá? et al. [J Instrum 4:10, 2009] with a 50% relative efficiency BEGe detector. 相似文献
117.
In this paper we study ergodic properties of some classes of anomalous diffusion processes. Using the recently developed measure of dependence called the Correlation Cascade, we derive a generalization of the classical Khinchin theorem. This result allows us to determine ergodic properties of Lévy-driven stochastic processes. Moreover, we analyze the asymptotic behavior of two different fractional Ornstein–Uhlenbeck processes, both originating from subdiffusive dynamics. We show that only one of them is ergodic. 相似文献
118.
Leszek Krzemień Krzysztof Brzozowski Marcin Witkowski Micha? Zawada 《Optics Communications》2011,284(5):1247-1253
We present a method of Doppler-free laser frequency stabilization based on magnetically assisted rotation spectroscopy (MARS) which combines the Doppler-free velocity-selective optical pumping (VSOP) and magnetic rotation spectroscopy. The stabilization is demonstrated for the atomic rubidium transitions at 780 nm. The proposed method is largely independent of stray magnetic fields and does not require any modulation of the laser frequency. Moreover, the discussed method allows one to choose between locking the laser exactly to the line center, or with a magnetically-controlled shift to an arbitrary frequency detuned by up to several natural linewidths. This feature is useful in many situations, e.g. for laser cooling experiments. In addition to presenting the principle of the method, its theoretical background and peculiarities inherent to the repopulation VSOP are discussed. 相似文献
119.
Sławomir Prucnal Marcin Turek Andrzej Drozdziel Krzysztof Pyszniak Artur Wójtowicz Sheng-Qiang Zhou Alohe Kanjilal Artem Shalimov Wolfgang Skorupa Jerzy Zuk 《Central European Journal of Physics》2011,9(2):338-343
The InAs quantum structures were formed in silicon by sequential ion implantation and subsequent thermal annealing. Two kinds of crystalline InAs nanostructures were successfully synthesized: nanodots (NDs) and nanopyramids (NPs). The peaks at 215 and 235 cm?1, corresponding to the transverse optical (TO) and longitudinal optical (LO) InAs single-phonon modes, respectively, are clearly visible in the Raman spectra. Moreover, the PL band at around 1.3 µm, due to light emission from InAs NDs with an average diameter 7±2 nm, was observed. The InAs NPs were found only in samples annealed for 20 ms at temperatures ranging from 1000 up to 1200°C. The crystallinity and pyramidal shape of InAs quantum structures were confirmed by HRTEM and XRD techniques. The average size of the NPs is 50 nm base and 50 nm height, and they are oriented parallel to the Si (001) planes. The lattice parameter of the NPs increases from 6.051 to 6.055 Å with the annealing temperature increasing from 1100 to 1200°C, due to lattice relaxation. Energy dispersive spectroscopy (EDS) shows almost stoichiometric composition of the InAs NPs. 相似文献
120.
We propose a method for defining and measuring spatial contagion between two financial markets via conditional copulas. Some theoretical results on monotonicity and asymptotic properties of Gaussian copulas with respect to conditioning are presented. Next, we combine the spatial contagion approach with time series models. We investigate which model from a large family of multivariate GARCH is the best tool for modelling spatial contagion. In an empirical study, we show that among models designed for general fit, a two‐step model fitting procedure reduces the ability to describe the contagion effect. This is a feature of copula‐GARCH models. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献