Comparison of the volatile profiles of Arzúa-Ulloa and Tetilla cheeses manufactured from raw and pasteurized milk

Levels of volatile compounds in Arzúa-Ulloa and Tetilla cheeses manufactured from raw and pasteurized milk were investigated. Analysis of volatile compounds in six raw milk (RM) starter-free cheeses (15–45 days old) and six pasteurized milk (PM) cheeses made with deliberately added starters (15–45 days old) manufactured in different dairies, was performed on an automatic dynamic headspace apparatus coupled to a GC/MS. The volatile fraction of RM cheeses displayed 46 volatile compounds (34 for PM cheeses) including fatty acids, esters, aldehydes, alcohols, ketones, hydrocarbons and sulphur compounds. Fatty acids and several esters were only detected in RM cheeses. Moreover, the highest contents of methylketones, secondary alcohols and branched-chain aldehydes and alcohols were also observed in RM cheeses. All results confirm more intense lipolysis in RM cheeses than in PM cheeses. In addition, branched-chain aldehydes and alcohols were significantly more abundant in RM than in PM cheeses, which indicates that catabolism of branched-chain amino acids was significantly higher in RM cheeses. This study has provided useful information which will allow the selection of starter and non-starter bacteria more suitable for manufacturing Arzúa-Ulloa and Tetilla pasteurized milk cheeses with organoleptic characteristics similar to those of traditional raw milk cheeses.     

Raman analysis of surimi gelation by addition of wheat dietary fibre

Raman analysis has been carried out to study the effects of Vitacel^® wheat dietary fibre (WDF) during gelation of surimi. The main results reveal the following: (a) Vitacel^® comprises natural cellulose I as major component; (b) hydration of WDF leads to νCH frequency upshifting and decreasing intensity. On the basis of these spectral features it is suggested that water transfer from protein to WDF can occur in surimi gels. WDF hydration can be interpreted in the sense that this fibre either takes water that is delivered from the gel protein upon heat-mediated formation of β-sheets and hydrophobic contacts and/or or acts as an active dehydrating agent. An increase of solvent-exposed hydrophobic side chains is observed in the sol phase, upon the addition of WDF, which may cause breaking of intermolecular protein hydrophobic contacts; a subsequent change upon WDF-containing gel formation is the reduction in the νCH intensity, which may be indicative of increasing hydrophobic WDF-protein contacts. Interestingly, these results constitute molecular data, to be considered when designing restructured fish products with these fibre ingredients.     

Magnetic interactions as a stabilizing factor of semiquinone species of lawsone by metal complexation

Changes in electrochemical reactivity for lawsone anions (lawsone, 2-hydroxy-1,4-naphthoquinone, HLw) being coordinated to a series of metallic ions in dimethylsulfoxide solution were evaluated. Upon performing cyclic voltammetry experiments for metal complexes of this quinone with pyridine (Py) - structural formula M(II)(Lw⁻)₂(Py)₂; M: Co(II), Ni(II), Zn(II) - it was found that the reduction of coordinated Lw⁻ units occurs during the first and second electron uptake in the analyzed compounds. The stability of the electrogenerated intermediates for each complex depends on the d electron configuration in each metal center and is determined by magnetic interactions with the available spins considering an octahedral conformation for all the compounds. This was evidenced by in situ spectroelectrochemical-ESR measurements in the Zn(II) complex in which due to the lack of magnetic interaction owing to its electron configuration, the structure of the coordinated anion radical species was determined. Successive reduction of the associated Lw⁻ units leads to partial dissociation of the complex, determined by the identification of free radical dianion structures in solution. These results show some insights on how metal-lawsone complexation can modify the solution reactivity and stability of the electrogenerated radical species.     

Continuous catalyst-free methanolysis and ethanolysis of soybean oil under supercritical alcohol/water mixtures

This work investigates and compares the reaction performance of soybean oil transesterification under supercritical methanol and ethanol, in a continuous catalyst-free process, as a cleaner alternative to conventional chemically catalyzed process. Reactions were performed in a tubular reactor, at 20 MPa, with oil to alcohol ratio of 1:40, varying the temperature in the range from 250 °C to 350 °C, and at two levels of water concentrations, 0 and 10 wt%. Although both processes proceeded with a relatively high reaction rate, conversion achieved by methanolysis was higher than that obtained by ethanolysis. Water positively affected both process: higher ester content and triacylglycerols depletion occurred when 10 wt% water was used compared with anhydrous conditions. Temperature increase favored the conversion of soybean oil to the corresponding methyl or ethyl esters, although temperatures above 300 °C increased the fatty acid degradation degree, a phenomenon responsible for the low ester contents obtained at the highest temperatures and lowest flow rates studied.     

Competition,regulation, and pricing behaviour in the Spanish retail gasoline market

The restructuring of the Spanish oil industry produced a highly concentrated oligopoly in the retail gasoline market. In June 1990, the Spanish government introduced a system of ceiling price regulation in order to ensure that “liberalization” was accompanied by adequate consumer protection. By 1998, prices were left to the “free” market. This paper examines the pricing behaviour of the retail gasoline market using multivariate error correction models over the period January 1993 (abolishment of the state monopoly)–December 2004. The results suggest that gasoline retail prices respond symmetrically to increases as well as to decreases in the spot price of gasoline both over the period of price regulation (January 1993–September 1998) and over the period of free market (October 1998–December 2004). However, once the ceiling price regulation was abolished, cooperation emerged between the government and the major operators, Repsol-YPF and Cepsa-Elf, to control the inflation rate. This resulted in a slower rate of adjustment of gasoline retail prices when gasoline spot prices went up, as compared with the European pattern. Finally, the Spanish retail margin was by the end of our timing period of analysis, as in the starting years after the abolishment of the state monopoly, above the European average. This pattern confirms our political economic hypothesis, which suggests that the Spanish government and the oil companies were working together in reducing the inflation, in periods of rising oil and gasoline prices. It is also inferred that explaining the pricing pattern in energy markets may require different hypothesis than the classical perspective, involving just firms taking advantage of market power.     

The Sonogel-Carbon electrode as a sol-gel graphite-based electrode

In this work, a novel sol-gel-based procedure to obtain solid carbon composite electrodes is proposed. The procedure is based on the use of sonocatalysis to apply high-energy ultrasound directly to the precursors; this way, ultrasonic cavitation is achieved so that hydrolysis with acidic water is promoted in the absence of any additional solvent and the time needed to get a unique phase is reduced drastically. The mix of sonogel with spectroscopic grade graphite leads to a new type of sol-gel electrode: the Sonogel-Carbon electrode. The amount of water, necessary for hydrolysis to occur, has been studied, as well as the sol pH value and the electrochemical behavior of the Sonogel-Carbon electrode in Britton-Robinson buffer. Mechanical renewal of the electrodes surfaces and background signal stability for at least 42 days have been also tested. We have carried out some tests to check the ability of the synthesized material to give electrochemical response when redox species are present in the background electrolyte. Mechanical and electrochemical studies indicate that the Sonogel-Carbon electrode shows good properties for use as an electrochemical sensor.     

Convergent optical correlator aligment based on frequency filtering

The convergent correlator is widely used but it presents the drawback of the alignment requirements: fine focusing of the input scene Fourier transform on the filter plane, filter centering, scaling the scene Fourier transform to match the filter size, and azimuth matching of the filter with the input scene. We propose a set of tests to obtain a precise alignment of the convergent correlator. These methods are based on frequency filtering properties and they are applicable either for amplitude input or for phase-encoded input. The tests we present allow us to fulfill all the alignment requirements. The theory on which these tests are based is explained. The experimental results obtained during the alignment procedure are presented. We show some additional verifications of the correct alignment of the convergent correlator.     

Blood speed imaging with an intraluminal array

In applications in which Doppler processing is not possible, such as side-looking intravascular imaging systems, decorrelation methods can be used to estimate blood speed. Here, a method is presented measuring relative blood speed using an FIR filter bank to estimate temporal decorrelation rates. It can be implemented in a modern commercially available ultrasound imaging system with no additional hardware. Both simulations and experiments using an intraluminal scanner appropriate for coronary artery applications have tested the system. In this study, the FIR filter bank is contrasted with previous methods, and its utility is further demonstrated with real-time color flow images from a pig model.     

Mode-specific strategy for controlling a single-molecule reaction

Inelastic tunnelling electrons are a proper excitation source to induce chemical transformations on a single adsorbate. When their energy is tuned to that of molecular vibrational states, the modification may follow complex internal vibrational pathways. Here, we analyse our recent results on the selective excitation of ammonium stretching or bending modes to control the outcome of a simple bond-cleavage reaction. With the help of model calculations, we provide a detailed molecular-scale picture of the competing internal pathways leading to molecular movement. A mode-selective strategy, based on local excitations of specific reaction coordinates, has an important drawback when applied to adsorbate systems due to the problem of fast energy randomization. The success of such a mode-selective strategy is determined here by the ability of the scanning tunnelling microscope to study reactivity in the limit of very low yield and very low power irradiation, in a regime where vibrational heating of the adsorbate/surface system becomes negligible.     

Modeling of zinc solubility in stabilized/solidified electric arc furnace dust

Equilibrium models which attempt for the influence of pH on the solubility of metals can improve the dynamic leaching models developed to describe the long-term behavior of waste-derived forms. In addition, such models can be used to predict the concentration of metals in equilibrium leaching tests at a given pH. The aim of this work is to model the equilibrium concentration of Zn from untreated and stabilized/solidified (S/S) electric arc furnace dust (EAFD) using experimental data obtained from a pH-dependence leaching test (acid neutralization capacity, ANC). EAFD is a hazardous waste generated in electric arc furnace steel factories; it contains significant amounts of heavy metals such as Zn, Pb, Cr or Cd. EAFD from a local factory was characterized by X-ray fluorescence (XRF), acid digestion and X-ray diffraction (XRD). Zn and Fe were the main components while the XRD analysis revealed that zincite, zinc ferrite and hematite were the main crystalline phases. Different cement/EAFD formulations ranging from 7 to 20% dry weight of cement were prepared and subjected to the ANC leaching test. An amphoteric behavior of Zn was found from the pH dependence test. To model this behavior, the geochemical model Visual MINTEQ (VMINTEQ) was used. In addition to the geochemical model, an empirical model based on the dissolution of Zn in the acidic zone and the re-dissolution of zinc compounds in the alkaline zone was considered showing a similar prediction than that obtained with VMINTEQ. This empirical model seems to be more appropriate when the metal speciation is unknown, or when if known, the theoretical solid phases included in the database of VMINTEQ do not allow to describe the experimental data.