Interaction of isobutene and methacrolein with silica-supported uranium and molybdenum oxide catalysts

The adsorption of isobutene (in the temperature range 309–341K) and methacrolein (in the temperature range 296–336 K) on a Mo/(Mo+U)=0.89 catalyst were studied. The equilibrium data were analysed according to Freundlich's model. The high coverages observed at lower temperatures suggest some participation of physical adsorption in the reversible adsorption. Entropy calculations showed that these adsorbed species are best described by a mobile model which assumes bidimensional translation and two rotational degrees of freedom. Isobutene is weakly chemisorbed, producing reversible species which were identified as a π-complex formed by interaction with surface OH groups through π-electrons (infrared bands at 1655, 1615, 1470 and 1375 cm^?1), and only a small fraction of isobutene interacts strongly via lattice oxygen forming intermediate species in the oxidation reaction. However, in the presence of oxygen at 523 K a majority of the surface species are strongly held by the surface (infrared bands at 1775, 1723, 1610, 1460 and 1350 cm^?1 associated to a methacrylic complex and bands at 1590 and 1538 cm^?1 of carbonate-carboxylate species).     

Effect of γ-radiation on green onion DNA integrity: Role of ascorbic acid and polyphenols against nucleic acid damage

The effect of γ-radiation on green onion DNA integrity, phenol content, oxygen radical absorbance capacity, employing pyrogallol red and fluorescein as probes, as well as ascorbic acid content has been evaluated. Measurements using thiazole orange-DNA fluorescence and agarose gel electrophoresis show that γ-radiation does not lead to an apparent DNA change in green onion. However, it was readily cleaved upon irradiation from the previously isolated nucleic acid. Furthermore, green onion exposure to γ-radiation produces slight increases in the polyphenol concentrations (163–188 μM Trolox eq.) and a decrease in the oxygen radical absorbance using fluorescein (from 245 to 200 Trolox eq.) Interestingly, a high ascorbic acid content (364 μM), which decreases by 40% after γ-ray exposure was measured by using pyrogallol-red-based oxygen radical absorbance capacity induction times from green onion aqueous extracts. Thus, our results suggest that ascorbic acid present in green onion plays a fundamental role in the plant antioxidant response toward γ-radiation exposure, while polyphenols remain largely unchanged, as revealed from oxygen radical absorbance capacity, employing pyrogallol red.     

Integrate-and-fire neurons driven by correlated stochastic input

Neurons are sensitive to correlations among synaptic inputs. However, analytical models that explicitly include correlations are hard to solve analytically, so their influence on a neuron's response has been difficult to ascertain. To gain some intuition on this problem, we studied the firing times of two simple integrate-and-fire model neurons driven by a correlated binary variable that represents the total input current. Analytic expressions were obtained for the average firing rate and coefficient of variation (a measure of spike-train variability) as functions of the mean, variance, and correlation time of the stochastic input. The results of computer simulations were in excellent agreement with these expressions. In these models, an increase in correlation time in general produces an increase in both the average firing rate and the variability of the output spike trains. However, the magnitude of the changes depends differentially on the relative values of the input mean and variance: the increase in firing rate is higher when the variance is large relative to the mean, whereas the increase in variability is higher when the variance is relatively small. In addition, the firing rate always tends to a finite limit value as the correlation time increases toward infinity, whereas the coefficient of variation typically diverges. These results suggest that temporal correlations may play a major role in determining the variability as well as the intensity of neuronal spike trains.     

Dynamic modeling of DC–DC converters with peak current control in double‐stage photovoltaic grid‐connected inverters

In photovoltaic (PV) double‐stage grid‐connected inverters a high‐frequency DC–DC isolation and voltage step‐up stage is commonly used between the panel and the grid‐connected inverter. This paper is focused on the modeling and control design of DC–DC converters with Peak Current mode Control (PCC) and an external control loop of the PV panel voltage, which works following a voltage reference provided by a maximum power point tracking (MPPT) algorithm. In the proposed overall control structure the output voltage of the DC–DC converter is regulated by the grid‐connected inverter. Therefore, the inverter may be considered as a constant voltage load for the development of the small‐signal model of the DC–DC converter, whereas the PV panel is considered as a negative resistance. The sensitivity of the control loops to variations of the power extracted from the PV panel and of its voltage is studied. The theoretical analysis is corroborated by frequency response measurements on a 230 W experimental inverter working from a single PV panel. The inverter is based on a Flyback DC–DC converter operating in discontinuous conduction mode (DCM) followed by a PWM full‐bridge single‐phase inverter. The time response of the whole system (DC–DC + inverter) is also shown to validate the concept. Copyright © 2011 John Wiley & Sons, Ltd.     

Dynamic modeling of a dual active bridge DC to DC converter with average current control and load‐current feed‐forward

Bidirectional power flow is needed in many power conversion systems like energy storage systems, regeneration systems, power converters for improvement of the power quality and some DC‐DC applications where bidirectional high power conversion and galvanic isolation are required. The dual active bridge (DAB) is an isolated, high voltage ratio DC‐DC converter suitable for high power density and high power applications, being a key interface between renewable energy sources and energy storage devices. This paper is focused on the modeling and control design of a DC‐DC system with battery storage based on a DAB converter with average current mode control of the output current and output voltage control. The dynamic response of the output voltage to load steps is improved by means of an additional load‐current feed‐forward control loop. An analytical study of the load‐current feed‐forward is presented and validated by means of both simulations and experimental results. Copyright © 2014 John Wiley & Sons, Ltd.     

Assessment of a Cylindrical and a Rectangular Plate Differential Mobility Analyzer for Size Fractionation of Nanoparticles at High-Aerosol Flow Rates

An existing differential mobility analyzer (DMA) of cylindrical electrodes and a novel DMA of rectangular plate electrodes are demonstrated for size fractionation of nanoparticles at high-aerosol flow rates in this work. The two DMAs are capable of delivering monodisperse size selected nanoparticles (SMPS σ_g < 1.1) at gas flow rates ranging from 200 slm to 500 slm. At an aerosol flow rate of 200 slm, the maximum attainable particle mean size is of about 20 nm for the cylindrical DMA and of nearly 50 nm for the rectangular plate DMA. The number concentration of the monodisperse nanoparticles delivered by the high-flow DMAs spans from 10⁴ cm^?3 to 10⁶ cm^?3 depending upon the particle mean size and particle size dispersion.

Copyright 2014 American Association for Aerosol Research     

Radiation-grafting of N,N-dimethylaminoethylmetacrylate onto polyethylene film by preirradiation method

Radiation-induced graft polymerization of N,N-dimethylaminoethyl-metacrylate onto low density polyethylene (LDPE) film by the preirradiation method in presence of air was investigated. The appropriate reaction conditions at which the graft polymerization was carried out are reported. Received: 4 December 1996/Revised: 5 March 1997/Accepted: 10 March 1997     

Reductive Amination Without the Aldehyde: Use of a Ketolactol as an Aldehyde Surrogate

To overcome stability issues associated with the use of an aldehyde in a catalytic reductive amination reaction, a cyclic ketolactol (ω-hydroxylactone) was employed as an aldehyde surrogate to form a γ-aminoacid. The reaction proceeded most favorably over a Pt/C catalyst. The thermodynamics of each step were evaluated using density functional theory calculations, which correctly predicted the dominance of the ring-closed lactol reactant, yet suggested a preference for a ring-opened iminium intermediate upon the initial, slightly endoergic addition of amine substrate. Exoergic hydrogenation of this intermediate provided the thermodynamic driving force for the overall transformation. During development, the reaction was observed to depend significantly on the volumetric gas to liquid mass transfer coefficient (k_La) and this parameter was optimized to ensure successful scale up in a 400 L stirred tank reactor.