Development of a CE-ESI-microTOF-MS method for a rapid identification of phenolic compounds in buckwheat

A sensitive CE-ESI-MS analytical method for the identification of buckwheat antioxidants has been developed. CE and ESI-TOF parameters (e.g. buffer composition and pH, sheath liquid composition, sheath liquid and gas flow rates, electrospray voltage) were optimized to obtain an optimal analytical separation and identification. The results confirmed the presence of phenolic acids, procyanidins and galloylated propelargonidins. The identification of swertiamacroside and 2-hydroxy-3-O-β-D-glucopyranosil-benzoic acid, found for the first time in our previous work, has been confirmed. Furthermore, 5,7,4'-trimethoxyflavan and dihydroxy-trimethoxyisoflavan have also been tentatively identified for the first time in buckwheat.     

Wettability increase by "corona" ionization

Experiments showing an increase in the wettability of a hydrophobic surface when using corona air ionization are shown. Photoluminiscence observations support the predictions of charge accumulation at the triple line and confirm previous experiments. In all of the experiments, the contact angle was in the saturation regime at a value smaller than that predicted by the condition of a zero value for the solid-liquid surface tension. The PDMS did not show any deterioration due to the corona exposure under the experimental conditions used. The contact angle is shown to increase with humidity.     

Complexation Equilibria and Determination of Stability Constants of Binary and Ternary Nickel(II) Complexes with Amino Acids (Glycine, α-Alanine, β-Alanine and Proline) and Dipicolinic Acid as Ligands

In this paper we report the formation of binary and ternary nickel(II) complexes involving dipicolinic acid (H₂Dipic) as the primary ligand and some selected amino acids {glycine (HGly), ?-alanine (H?-Ala), ??-alanine (H??-Ala) and proline (HPro)} as secondary ligands. These complexes were studied at 25?°C by means of electromotive force measurements, emf(H), using 1.0?mol?dm^?3 NaCl as the ionic medium. The experimental data were analyzed by means of the computational least-squares program LETAGROP, taking into account hydrolysis of the nickel(II) cation and the acid/base reactions of the ligands whose equilibrium constants were kept fixed during the analysis. In the study of the binary nickel(II)?Camino acids systems the species [NiL]⁺, NiL₂ and [NiL₃]^? were observed, and in the case of the ternary nickel(II)?Cdipicolinic acid?Camino acids systems the complexes Ni(Dipic)HL, [Ni(Dipic)L] ^? and [Ni(Dipic)L(OH)]^2? were observed. The respective stability constants were determined, and the species distribution diagrams, as a function of pH, are briefly discussed.     

Opinion Dynamics with Disagreement and Modulated Information

Opinion dynamics concerns social processes through which populations or groups of individuals agree or disagree on specific issues. As such, modelling opinion dynamics represents an important research area that has been progressively acquiring relevance in many different domains. Existing approaches have mostly represented opinions through discrete binary or continuous variables by exploring a whole panoply of cases: e.g. independence, noise, external effects, multiple issues. In most of these cases the crucial ingredient is an attractive dynamics through which similar or similar enough agents get closer. Only rarely the possibility of explicit disagreement has been taken into account (i.e., the possibility for a repulsive interaction among individuals’ opinions), and mostly for discrete or 1-dimensional opinions, through the introduction of additional model parameters. Here we introduce a new model of opinion formation, which focuses on the interplay between the possibility of explicit disagreement, modulated in a self-consistent way by the existing opinions’ overlaps between the interacting individuals, and the effect of external information on the system. Opinions are modelled as a vector of continuous variables related to multiple possible choices for an issue. Information can be modulated to account for promoting multiple possible choices. Numerical results show that extreme information results in segregation and has a limited effect on the population, while milder messages have better success and a cohesion effect. Additionally, the initial condition plays an important role, with the population forming one or multiple clusters based on the initial average similarity between individuals, with a transition point depending on the number of opinion choices.     

Assignments of Carbon-Sulphur Vibrations by Selenation: An FT-IR and FT-Raman Study on 1, 3, 5-Trithiacyclohexane

Abstract

The IR and Raman spectra of 1, 3, 5-trithiacyclohexane (1) and 1, 3, 5-triselenocyclohexane (2) have been recorded with FT-instrumentation within 3500–100 cm^?l, and the C-S vibrations of 1 have been reviewed by comparing its spectra with those of 2. The IR and Raman spectra slightly differ from those previously reported and some vibrations, previously assigned to C-H modes in 1on the basis of NCT calculations, are reassigned to C-S modes on the basis of the selenation effect. “Selenation” has proved to be a very simple and effective tool in recognizing carbon-sulfur vibrations both in IR and Raman. The Raman peaks due to carbon-chalcogen vibrations are less intense in 1 than in 2, according to the higher polarizability of the selenium atom.     

On sets of type (q + 1, n)2 in finite three-dimensional projective spaces

It is proved that a k–set of type (q + 1, n)₂ in PG(3, q) either is a plane or it has size k ≥ (q + 1)² and a characterization of some sets of size (q + 1)² is given.     

Unexpected copper(II) catalysis: catalytic amine base promoted β-borylation of α,β-unsaturated carbonyl compounds in water

Using bis(pinacolato)diboron, catalytic amounts of Cu(II), and various amine bases in water under atmospheric conditions at rt, acyclic and cyclic α,β-unsaturated ketones and esters are β-borylated in up to 98% yield. Mechanistic investigations using UV-vis spectroscopy, (11)B NMR, and solvent kinetic isotope effect suggest that the role of the amine is not only to coordinate to Cu(II) but also to activate a nucleophilic water molecule to form the reactive sp(2)-sp(3) diboron complex.     

Components in time-varying graphs

Real complex systems are inherently time-varying. Thanks to new communication systems and novel technologies, today it is possible to produce and analyze social and biological networks with detailed information on the time of occurrence and duration of each link. However, standard graph metrics introduced so far in complex network theory are mainly suited for static graphs, i.e., graphs in which the links do not change over time, or graphs built from time-varying systems by aggregating all the links as if they were concurrent in time. In this paper, we extend the notion of connectedness, and the definitions of node and graph components, to the case of time-varying graphs, which are represented as time-ordered sequences of graphs defined over a fixed set of nodes. We show that the problem of finding strongly connected components in a time-varying graph can be mapped into the problem of discovering the maximal-cliques in an opportunely constructed static graph, which we name the affine graph. It is, therefore, an NP-complete problem. As a practical example, we have performed a temporal component analysis of time-varying graphs constructed from three data sets of human interactions. The results show that taking time into account in the definition of graph components allows to capture important features of real systems. In particular, we observe a large variability in the size of node temporal in- and out-components. This is due to intrinsic fluctuations in the activity patterns of individuals, which cannot be detected by static graph analysis.     

Comparison between XRF and EPMA applied to study the ionic exchange in zeolites

Zeolites are crystalline aluminosilicates consisting of SiO₄ and AlO₄ tetrahedral as primary units. One peculiar characteristic of zeolites is the ion exchange capacity defined as the capacity to locate specific cations in the framework of zeolites; it depends on the chemical composition and varies with the structure of the zeolite and with the cation nature. This work studies the exchange of the Na⁺ monovalent cation of 5A and 13X synthetic zeolites by the Ca²⁺ bivalent cation present in a CaCl₂ solution. X‐ray fluorescence (XRF) and electron probe microanalysis (EPMA) techniques were used to determine the cation exchange capacity (CEC). The efficiencies of the two X‐ray detectors were compared and the minimum detection limits of the zeolite elements were calculated. Although both techniques differ in the sample excitation mode, the results obtained were compatible. The results showed that the CEC was higher for the 5A zeolite, in agreement with its lower SiO₂/Al₂O₃ ratio and its greater BET area. It was also found that the amount of Na⁺ ions exchanged by Ca²⁺ ions was in complete agreement with the corresponding molar balance. The determination of the CEC using X‐ray spectroscopy techniques can be considered a novelty as XRF and EPMA techniques permit to analyze the sample directly. Copyright © 2009 John Wiley & Sons, Ltd.