Fano versus Kondo resonances in a multilevel "semiopen" quantum dot

Linear conductance across a large quantum dot via a single level epsilon(0) with large hybridization to the contacts is strongly sensitive to quasibound states localized in the dot and weakly coupled to epsilon(0). The conductance oscillates with the gate voltage due to interference of the Fano type. At low temperature and Coulomb blockade, Kondo correlations damp the oscillations on an extended range of gate voltage values, by freezing the occupancy of the epsilon(0) level itself. As a consequence, the antiresonances of Fano origin are washed out. The results are in good correspondence with experimental data for a large quantum dot in the semiopen regime.     

Instabilities of micellar systems under homogeneous and non-homogeneous flow conditions

The rheological behavior of a cetylpyridinium chloride 100 mmol l^–1/sodium salicylate 60 mmol l^–1 aqueous solution was studied in this work under homogeneous (cone and plate) and non-homogeneous flow conditions (vane-bob and capillary rheometers), respectively. Instabilities consistent with non-monotonic flow curves were observed in all cases and the solution exhibited similar behavior under the different flow conditions. Hysteresis and the sigmoidal flow curve suggested as characteristic of systems that show constitutive instabilities were observed when running cycles of increasing and decreasing stress or shear rate, respectively. This information, together with a detailed determination of steady states at shear stresses close to the onset of the instabilities, allowed one to show unequivocally that "top and bottom jumping" are the mechanisms to trigger the instabilities in this micellar system. It is shown in addition that there is not a true plateau region in between the "top and bottom jumping". Finally, the flow behavior beyond the upturn seemed to be unstable and was found accompanied by an apparent violation of the no-slip boundary condition.     

Experimental implementation of a low-frequency global sound equalization method based on free field propagation

An experimental implementation of a global sound equalization method in a rectangular room using active control is described in this paper. The main purpose of the work has been to provide experimental evidence that sound can be equalized in a continuous three-dimensional region, the listening zone, which occupies a considerable part of the complete volume of the room. The equalization method, based on the simulation of a progressive plane wave, was implemented in a room with inner dimensions of 2.70 m × 2.74 m × 2.40 m. With this method, the sound was reproduced by a matrix of 4 × 5 loudspeakers in one of the walls. After traveling through the room, the sound wave was absorbed on the opposite wall, which had a similar arrangement of loudspeakers, by means of active control. A set of 40 digital FIR filters was used to modify the original input signal before it was fed to the loudspeakers, one filter for each transducer. The optimal arrangement of the loudspeakers and the maximum frequency that can be equalized is analyzed theoretically in this paper. The presented experimental results show that sound equalization was possible from 10 Hz to approximately 425 Hz in the listening zone. A flat frequency response with deviations within ±5 decibels from the desired value was achieved. A higher demanding performance with deviations within ±1.5 decibels from a flat frequency response was attained in the interval between 20 Hz and 280 Hz. At the same time, the impulse response was quite well approximated to a delayed delta function in the listening zone. Examples of the spatial distribution of the sound field are also shown.     

Unmanned platform for long-range remote analysis of volatile compounds in air samples

This paper describes a long-range remotely controlled CE system built on an all-terrain vehicle. A four-stroke engine and a set of 12-V batteries were used to provide power to a series of subsystems that include drivers, communication, computers, and a capillary electrophoresis module. This dedicated instrument allows air sampling using a polypropylene porous tube, coupled to a flow system that transports the sample to the inlet of a fused-silica capillary. A hybrid approach was used for the construction of the analytical subsystem combining a conventional fused-silica capillary (used for separation) and a laser machined microfluidic block, made of PMMA. A solid-state cooling approach was also integrated in the CE module to enable controlling the temperature and therefore increasing the useful range of the robot. Although ultimately intended for detection of chemical warfare agents, the proposed system was used to analyze a series of volatile organic acids. As such, the system allowed the separation and detection of formic, acetic, and propionic acids with signal-to-noise ratios of 414, 150, and 115, respectively, after sampling by only 30 s and performing an electrokinetic injection during 2.0 s at 1.0 kV.     

New Hg2+ and Cu2+ selective chromo- and fluoroionophore based on a bichromophoric azine

[graph: see text] A new probe, 1,4-bis(1-pyrenyl)-2,3-diaza-1,3-butadiene, selectively senses Hg2+ and Cu2+ through two different channels: the yellow-deep-pink color change and the enhancement of the fluorescence with the red shift of the excimer emission, which can visually be discernible by a green fluorescence in the presence of Hg2+ and an orange fluorescence in the presence of Cu2+.     

The Relevance of the Collaborative Effect in Determining the Performances of Photorefractive Polymer Materials

A derivative of 2‐methylindole, 3‐[2‐(4‐nitrophenyl)ethenyl]‐1‐allyl‐2‐methylindole, NPEMI‐A, is studied for its photoconductivity and photorefractivity behaviour. Its blends with the organic polymer poly‐(2,3‐dimethyl‐N‐vinylindole), PVDMI, are also investigated. Due to the expected and devised mutual solubility of the two components of the blends, it is possible to carry out measurements with the weight percent of the chromophore NPEMI‐A changing from zero to 100. Films were produced by a squeezing process between two ITO‐covered glass sheets. No opacity phenomena, that are so common for many other organic blends due to the segregation of the dissolved chromophore, are observed. The photorefractive optical gain Γ₂ is obtained as a function of the chromophore content. Differential scanning calorimetry measurements (DSC) are also carried out to obtain the whole change of the glass transition temperature T_g as a function of the amount of chromophore contained in the blends. From the experimental trend of T_g a meaningful quantitative estimate of the value of the electrostatic interactions acting in the studied blends, is obtained. The importance of the value of T_g, and of the electrostatic interactions, in determining the extent of the photorefractivity is clearly evident. The results are compared for NPEMI‐A (Γ₂=210 cm^?1) and for NPEMI‐E (Γ₂ ≈ 2000 cm^?1) that has a N‐2‐ethylhexyl group instead of a N‐allyl group. The Pockels and Kerr contributions and—for the first time—a “collaborative effect” of the photorefractivity of NPEMI‐A are distinguished and quantitatively evaluated.     

Chemical constituents of the bark of Dipteryx alata vogel, an active species against Bothrops jararacussu venom

The effect of four sub-extracts prepared from the lyophilized hydroalcoholic bark of Dipteryx alata (Leguminosae-Papilionoideae) dissolved in a methanol-water (80:20) mixture through a liquid-liquid partition procedure has been investigated against the neuromuscular blockade of the venom of the snake Bothrops jararacussu. The active CH?Cl? sub-extract has been extensively analyzed for its chemical constituents, resulting in the isolation of four lupane-type triterpenoids: lupeol, lupenone, 28-hydroxylup-20(29)-en-3-one, betulin, nine isoflavonoids: 8-O-methylretusin, 7-hydroxy-5,6,4'-trimethoxyisoflavone, afrormosin, 7-hydroxy-8,3',4'-trimethoxyisoflavone, 7,3'-dihydroxy-8,4'-dimethoxyisoflavone, odoratin, 7,8,3'-trihydroxy-4'-methoxyisoflavone, 7,8,3'-trihydroxy-6,4'-dimethoxyisoflavone, dipteryxin, one chalcone: isoliquiritigenin, one aurone: sulfuretin and three phenolic compounds: vanillic acid, vanillin, and protocatechuic acid. Their chemical structures were elucidated on the basis of spectroscopic analysis, including HRMS, 1D- and 2D-NMR techniques.     

Mechanism of multi‐metal(loid) methylation and hydride generation by methylcobalamin and cob(I)alamin: a side reaction of methanogenesis

Metal(loid)s are subject to many transformation processes in the environment, such as oxidation, reduction, methylation and hydride generation, predominantly accomplished by prokaryotes. Since these widespread processes affect the bioavailability and toxicity of metal(loid)s to a large extent, the investigation of their formation is of high relevance. Methanogenic Archaea are capable of methylating and hydrogenating Group 15 and 16 metal(loid)s arsenic, selenium, antimony, tellurium, and bismuth due to side reactions between central methanogenic cofactors, methylcobalamin (CH₃Cob(III)) and cob(I)alamin (Cob(I)). Here, we present systematic mechanistic studies on methylation and hydride generation of Group 15 and 16 metal(loid)s by CH₃Cob(III) and Cob(I). Pentavalent arsenical species showed neither methylation nor reduction as determined by using a newly developed oxidation state specific hydride generation technique, which allows direct determination of tri‐ and pentavalent arsenic species in a single batch. In contrast, efficient methylation of trivalent species without a change in oxidation state indicated that the methyl transfer does not proceed via a Challenger‐like oxidative methylation, but via a non‐oxidative methylation. Our findings also point towards a similar mechanism for antimony, bismuth, selenium, and tellurium. Overall, we suggest that the transfer of a methyl group does not involve a free reactive species, such as a radical, but instead is transferred either in a concerted nucleophilic substitution or in a caged radical mechanism. For hydride generation, we propose the intermediate formation of hydridocobalamin, transferring a hydride ion to the metal(loid)s. Copyright © 2012 John Wiley & Sons, Ltd.     

Dendritic effect in polymer-supported catalysis of the intramolecular Pauson-Khand reaction

A remarkable increase in catalytic activity and selectivity in the intramolecular Pauson-Khand reaction is observed for Co complexes, immobilised on second- and third-generation dendron-functionalized polystyrene, as compared with their analogues on non-dendronized support.