Complex dynamical behavior in the oxidation of hydroxylamine by bromate

Complex dynamical behavior has been observed in the oxidation of hydroxylamine by bromate in acidic sulfate medium. The reaction shows clock type kinetics in closed conditions and an aperiodic oscillations if gaseous products are removed from the system with a constant flow-rate. The reduction kinetics of bromate ions with excess hydroxylamine has been studied in the presence of allyl alcohol. The observed pseudo-first-order rate constant k_obs has been found to follow the expression where [hydroxylamine] is total initial hydroxylamine concentration, K₁ = 0.5 M^?1, K₂ = 10⁶ M^?1, and k = 2.57 × 10³ M^?1 s^?1 at 298.15 K and I = 2.0 M. The rate constant for the bromine oxidation of hydroxylamine in sulfuric aqueous solution has been determined. © 1994 John Wiley & Sons, Inc.     

Superintegrable models on Riemannian surfaces of revolution with integrals of any integer degree (I)

We present a family of superintegrable (SI) systems which live on a Riemannian surface of revolution and which exhibit one linear integral and two integrals of any integer degree larger or equal to 2 in the momenta. When this degree is 2, one recovers a metric due to Koenigs.The local structure of these systems is under control of a linear ordinary differential equation of order n which is homogeneous for even integrals and weakly inhomogeneous for odd integrals. The form of the integrals is explicitly given in the so-called “simple” case (see Definition 2). Some globally defined examples are worked out which live either in H² or in R².     

Locking of Turing patterns in the chlorine dioxide-iodine-malonic acid reaction with one-dimensional spatial periodic forcing

We use the photosensitive chlorine dioxide-iodine-malonic acid reaction-diffusion system to study wavenumber locking of Turing patterns with spatial periodic forcing. Wavenumber-locked stripe patterns are the typical resonant structures that labyrinthine patterns exhibit in response to one-dimensional forcing by illumination when images of stripes are projected on a working medium. Our experimental results reveal that segmented oblique, hexagonal and rectangular patterns can also be obtained. However, these two-dimensional resonant structures only develop in a relatively narrow range of forcing parameters, where the unforced stripe pattern is in close proximity to the domain of hexagonal patterns. Numerical simulations based on a model that incorporates the forcing by illumination using an additive term reproduce well the experimental observations. These findings confirm that additive one-dimensional forcing can generate a two-dimensional resonant response. However, such a response is considerably less robust than the effect of multiplicative forcing.     

Experimental design for extraction and quantification of phenolic compounds and organic acids in white "Vinho Verde" grapes

An experimental design was applied for the optimization of extraction and clean-up processes of phenolic compounds and organic acids from white “Vinho Verde” grapes. The developed analytical method consisted in two steps: first a solid-liquid extraction of both phenolic compounds and organic acids and then a clean-up step using solid-phase extraction (SPE). Afterwards, phenolic compounds and organic acids were determined by high-performance liquid chromatography (HPLC) coupled to a diode array detector (DAD) and HPLC-UV, respectively. Plackett-Burman design was carried out to select the significant experimental parameters affecting both the extraction and the clean-up steps. The identified and quantified phenolic compounds were: quercetin-3-O-glucoside, quercetin-3-O-rutinoside, kaempferol-3-O-rutinoside, isorhamnetin-3-O-glucoside, quercetin, kaempferol and epicatechin. The determined organic acids were oxalic, citric, tartaric, malic, shikimic and fumaric acids. The obtained results showed that the most important variables were the temperature (40 °C) and the solvent (acid water at pH 2 with 5% methanol) for the extraction step and the type of sorbent (C18 non end-capped) for the clean-up step.     

Solid-phase extraction versus matrix solid-phase dispersion: Application to white grapes

The use of matrix solid-phase dispersion (MSPD) was tested to, separately, extract phenolic compounds and organic acids from white grapes. This method was compared with a more conventional analytical method previously developed that combines solid liquid extraction (SL) to simultaneously extract phenolic compounds and organic acids followed by a solid-phase extraction (SPE) to separate the two types of compounds. Although the results were qualitatively similar for both techniques, the levels of extracted compounds were in general quite lower on using MSPD, especially for organic acids. Therefore, SL-SPE method was preferred to analyse white “Vinho Verde” grapes. Twenty samples of 10 different varieties (Alvarinho, Avesso, Asal-Branco, Batoca, Douradinha, Esganoso de Castelo Paiva, Loureiro, Pedernã, Rabigato and Trajadura) from four different locations in Minho (Portugal) were analysed in order to study the effects of variety and origin on the profile of the above mentioned compounds. Principal component analysis (PCA) was applied separately to establish the main sources of variability present in the data sets for phenolic compounds, organic acids and for the global data. PCA of phenolic compounds accounted for the highest variability (77.9%) with two PCs, enabling characterization of the varieties of samples according to their higher content in flavonol derivatives or epicatechin. Additionally, a strong effect of sample origin was observed. Stepwise linear discriminant analysis (SLDA) was used for differentiation of grapes according to the origin and variety, resulting in a correct classification of 100 and 70%, respectively.     

Dynamik des Blasenwachstums und Wärmeübergangs beim Sieden binärer Gemische von Äthylalkohol—Wasser

Measurements of bubble growth rate, detachment diameter and heat-transfer are reported for nucleate boiling of binary mixtures in various concentrations on a horizontal heating surface. The growth rate, characterized by the Jakob-number exhibits maximum at 30% (mass) ethylalcohol in the liquid phase. At this concentration the smallest heat transfer coefficient was measured. For growth rate this proves an influence of mass transfer across the phase boundary besides hydrodynamic and thermal effects.     

Surface Behavior of Polyamide 6 Modified by Barrier Plasma in Oxygen and Nitrogen

Polyamide (PA) 6 was modified by diffuse coplanar surface barrier discharge (DCSBD) plasma in an atmosphere of nitrogen and oxygen. The surface roughness decrease of PA 6 was detected by AFM and nano-indentation after modification in DCSBD plasma. A significant increase in O/C and N/C ratios of plasma-modified PA 6 using XPS analysis was found. The results show the importance of introducing oxygenic polar functional groups on the polymeric surface in order to increase its surface energy during a short time of plasma activation. The modification of PA 6 by DCSBD oxygen plasma was more efficient than by nitrogen plasma.     

Some Cubic Birth and Death Processes and their Related Orthogonal Polynomials

The orthogonal polynomials with recurrence relation (λ,_n +μ_n-z)F_n(z) = μ_n+1F_n+1(z)+λ_n-1F_n-1(z) with two kinds of cubic transition rates λ_n and μ_n, corresponding to indeterminate Stieltjes moment problems, are analyzed. We derive generating functions for these two classes of polynomials, which enable us to compute their Nevanlinna matrices. We discuss the asymptotics of the Nevanlinna matrices in the complex plane.     

Quantification of iodide and sodium-iodide symporter inhibitors in human urine using ion chromatography tandem mass spectrometry

We developed a sensitive and selective method for quantifying nitrate, thiocyanate, perchlorate and iodide in human urine using ion chromatography coupled with electrospray ionization tandem mass spectrometry. Analysis of proficiency testing materials and spiked urine indicates that the method is precise (coefficients of variation <5%) and accurate (relative percent differences <7.9%). Analytical response was linear across the physiologically relevant concentration range for the analytes, and adequately sensitive to quantify the analytes in >99% of urine samples tested. Measurement of these four toxicologically-related analytes in one assay will provide useful information for assessing potential linkage between exposure and health effects.     

Structural characterization of phenolics and betacyanins in Gomphrena globosa by high-performance liquid chromatography-diode array detection/electrospray ionization multi-stage mass spectrometry

The metabolite profiling of Gomphrena globosa inflorescences was performed by high-performance liquid chromatography-diode array detection/electrospray ionization multi-stage mass spectrometry (HPLC-DAD/ESI-MS(n)). Based on the fragmentation patterns, 24 phenolic compounds were characterized. The identified phenolics include p-coumaric and ferulic acids, quercetin, kaempferol, isorhamnetin, and hydroxylated 6,7-methylenedioxyflavone derivatives, as well as their aglycones, none of them reported before in the species. This is also the first time that tetrahydroxy-methylenedioxyflavone derivatives and acetylglycosides are described in nature. Betacyanins were also found. This study significantly extends the knowledge of the G. globosa metabolome, by providing further insights into its phenolic composition.