Multiresidue determination of 11 new fungicides in grapes and wines by liquid–liquid extraction/clean-up and programmable temperature vaporization injection with analyte protectants/gas chromatography/ion trap mass spectrometry

A gas chromatographic ion trap mass spectrometry (GC-ITMS) method was developed for the determination of 11 new generation fungicides (benalaxyl, benalaxyl-M, boscalid, cyazofamid, famoxadone, fenamidone, fluquinconazole, iprovalicarb, pyraclostrobin, trifloxystrobin and zoxamide) in grapes and wines. Samples were extracted with ethyl acetate:hexane (1:1, v/v) and cleaned-up with graphitized carbon black/primary secondary amine (GCB/PSA) solid-phase extraction (SPE) cartridges using acetonitrile:toluene (3:1, v/v) as eluent. The addition of analyte protectants (3-ethoxy-1,2-propanediol, d-sorbitol and l-gulonic acid γ-lactone) in the final extracts allowed to avoid the matrix-induced response enhancement effect on quantitation process with absolute recoveries ca. 100%. Precision (expressed as relative standard deviation) was lower than 16% for all fungicides. Limits of detection and quantitation were lower than 0.01 mg/kg or mg/L, except for cyazofamid, much smaller in all cases than maximum residue levels (MRLs) established by European Union for grapes and by Switzerland and Italy for wines. The proposed method was applied to determine fungicide residues in three different white grapes for vinification produced in Ribeiro area in Galicia (NW Spain), as well as in their corresponding final wines.     

The method of interpolating integral equations for quantum Fluids.—III

Summary A method for interpolating between the (F)HNC and (F)PY approaches in order to take into account elementary contributions has been presented in two preceding papers concerned with the properties of zero-temperature quantum fluids, described by short-range correlated wave functions. In the present paper, both for Bose and for Fermi systems, the technique is extended to the case in which the two-body radial distribution function contains a long-range tail, going asr ⁻⁴. The results obtained for the energy per particle and momentum distribution of liquid⁴He, polarized hydrogen and³He are presented in correspondence to variational wave functions containing only two-particle correlations.

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Riassunto In due precedenti lavori è stata sviluppata una tecnica di interpolazione tra le approssimazioni (F)HNC e (F)PY per tenere conto dei cosiddetti contributi elementari nel calcolo delle proprietà dei fluidi quantistici a temperatura zero e descritti da funzioni d’onda con fattori di correlazione a corto raggio. Nel presente lavoro il metodo è esteso, per sistemi sia bosonici che fermionici, al caso in cui la funzione radiale di distribuzione contenga una coda con andamentor ⁻⁴. Sono presentati i risultati ottenuti per l’energia per particella e la distribuzione di quantità di moto dell’⁴He liquido, dell’idrogeno polarizzato e dell’³He liquido, in corrispondenza a funzioni d’onda variazionali contenenti solo correlazioni di coppia.

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Резюме В двух предыдущих работах был предложен метод интерполяции между (F)HNC и (F)PY подходами. В этих работах рассматривались свойства квантовых жидкостей при нулевой температуре, которые описываются волновыми функциями с короткодействующими корреляциями. В данной работе, для Бозеи Ферми-систем, предложенная тенхика обобщается на случай, когда двух-частичная радиальная функция распределения содержит длиннодействующий хвост, который спадает какr ⁻⁴. Приводятся результаты для энергии на одну частицу и импульсное распределение для жидкого⁴He, поляризованного водорода и³H, причем соответствующие вариационные волновые функции содержат только двух-частичные корреляции.

     

Infinitesimal deformations of restricted simple Lie algebras I

We compute the infinitesimal deformations of two families of restricted simple modular Lie algebras of Cartan-type: the Witt–Jacobson and the Special Lie algebras.     

Extended Hyperspherical-Harmonic Expansion Bases

 The use of overcomplete expansion basis functions can be useful for reproducing important details of the structure of a few-particle system by a relatively small number of basis functions. The case considered in this paper is the hyperspherical harmonic basis which is complete but gives slow convergence patterns in constructing the wave functions of systems with interactions that change rapidly with the interparticle distances. The problem is investigated here for the three-nucleon ground state and a number of NN potential models. A faster convergence is obtained by enlarging the hyperspherical harmonic basis in a simple way. Such a behavior should also be important for calculations of the bound state of larger systems and of breakup scattering states. Received December 30, 1998; accepted for publication February 19, 1999     

Wavelet expansions forBMOρ (w)‐functions

We give necessary and sufficient conditions on the wavelet coefficients of a function for being a member of some BMO_φ (w) space. We achieve this characterization for a wide variety of wavelet systems. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electrocyclic [1,5] hydrogen shift in the thermal elimination kinetics of phenyl acetate and p-tolyl acetate in the gas phase: a density functional theory study

The kinetics and mechanisms of thermal decomposition of phenyl acetate and p-tolyl acetate in the gas phase were studied by means of electronic structure calculations using density functional theory methods: B3LYP/6-31G(d,p), B3LYP/6-31++G(d,p), B3PW91/6-31G(d,p), B3PW91/6-31++G(d,p), MPW1PW91/6-31G(d,p), MPW1PW91/6-31++G(d,p), PBE/6-31G(d,p) and PBE/6-31++G(d,p). Two possible mechanisms have been considered: mechanism A is a stepwise process involving electrocyclic [1,5] hydrogen shift to eliminate ketene through concerted six-membered cyclic transition-state structure, followed by tautomerisation of cyclohexadienone or by 4-methyl cyclohexadienone intermediate to give the corresponding phenol. Mechanism B is a one-step concerted [1,3] hydrogen shift through a four-membered cyclic transition-state geometry, to produce ketene and phenol or p-cresol. Theoretical calculations showed reasonable agreement with experimental activation parameters when using the Perdew, Burke and Ernserhof (PBE)functional, through the stepwise [1,5] hydrogen-shift mechanism. For mechanism B, large deviation for the entropy of activation was observed. No experimental data were available for p-tolyl acetate; however, theoretical calculations showed similar results to phenyl acetate, thus supporting the stepwise mechanism for both phenyl acetate and p-tolyl acetate.     

Robust pair‐copula based forecasts of realized volatility

A useful application for copula functions is modeling the dynamics in the conditional moments of a time series. Using copulas, one can go beyond the traditional linear ARMA (p,q) modeling, which is solely based on the behavior of the autocorrelation function, and capture the entire dependence structure linking consecutive observations. This type of serial dependence is best represented by a canonical vine decomposition, and we illustrate this idea in the context of emerging stock markets, modeling linear and nonlinear temporal dependences of Brazilian series of realized volatilities. However, the analysis of intraday data collected from e‐markets poses some specific challenges. The large amount of real‐time information calls for heavy data manipulation, which may result in gross errors. Atypical points in high‐frequency intraday transaction prices may contaminate the series of daily realized volatilities, thus affecting classical statistical inference and leading to poor predictions. Therefore, in this paper, we propose to robustly estimate pair‐copula models using the weighted minimum distance and the weighted maximum likelihood estimates (WMLE). The excellent performance of these robust estimates for pair‐copula models are assessed through a comprehensive set of simulations, from which the WMLE emerged as the best option for members of the elliptical copula family. We evaluate and compare alternative volatility forecasts and show that the robustly estimated canonical vine‐based forecasts outperform the competitors. Copyright © 2013 John Wiley & Sons, Ltd.     

Selecting green suppliers based on GSCM practices: Using fuzzy TOPSIS applied to a Brazilian electronics company

Due to an increased awareness and significant environmental pressures from various stakeholders, companies have begun to realize the significance of incorporating green practices into their daily activities. This paper proposes a framework using Fuzzy TOPSIS to select green suppliers for a Brazilian electronics company; our framework is built on the criteria of green supply chain management (GSCM) practices. An empirical analysis is made, and the data are collected from a set of 12 available suppliers. We use a fuzzy TOPSIS approach to rank the suppliers, and the results of the proposed framework are compared with the ranks obtained by both the geometric mean and the graded mean methods of fuzzy TOPSIS methodology. Then a Spearman rank correlation coefficient is used to find the statistical difference between the ranks obtained by the three methods. Finally, a sensitivity analysis has been performed to examine the influence of the preferences given by the decision makers for the chosen GSCM practices on the selection of green suppliers. Results indicate that the four dominant criteria are Commitment of senior management to GSCM; Product designs that reduce, reuse, recycle, or reclaim materials, components, or energy; Compliance with legal environmental requirements and auditing programs; and Product designs that avoid or reduce toxic or hazardous material use.     

Gaps in the poset of projections in the Calkin algebra

We study the gap structure of the partial order of projections of the Calkin algebra of a complex, separable, infinite-dimensional Hilbert space. We prove the existence of an analytic Hausdorff gap in this partial order. As a consequence we obtain that under Todorcevic’s Axiom and MA the gap spectrum of P(C(H)) is strictly bigger than the gap spectrum of P(ω)/Fin.