A three‐phase solvent extraction system combined with deep eutectic solvent‐based dispersive liquid–liquid microextraction for extraction of some organochlorine pesticides in cocoa samples prior to gas chromatography with electron capture detection

A sample pretreatment method based on the combination of a three‐phase solvent extraction system and deep eutectic solvent‐based dispersive liquid–liquid microextraction has been introduced for the extraction of four organochlorine pesticides in cocoa samples before their determination by gas chromatography‐electron capture detection. A mixture of sodium chloride, acetonitrile, and potassium hydroxide solution is added to cocoa bean or powder. After vortexing and centrifugation of the mixture, the collected upper phase (acetonitrile) is removed and mixed with a few microliters of N,N‐diethanol ammonium chloride: pivalic acid deep eutectic solvent. Then it is rapidly injected into deionized water and a cloudy solution is obtained. Under optimum conditions, the limits of detection and quantification were found to be 0.011‐0.031 and 0.036‐0.104 ng/g, respectively. The obtained extraction recoveries varied between 74 and 92%. Also, intra‐ (n = 6) and interday (n = 4) precisions were less than or equal to 7.1% for the studied pesticides at a concentration of 0.3 ng/g of each analyte. The suggested method was applied to determine the studied organochlorine pesticide residues in various cocoa powders and beans gathered from groceries in Tabriz city (Iran) and aldrin and dichlobenil were found in some of them.     

A modified pseudospectral method for solving trajectory optimization problems with singular arc

This paper presents a direct method based on Legendre–Radau pseudospectral method for efficient and accurate solution of a class of singular optimal control problems. In this scheme, based on a priori knowledge of control, the problem is transformed to a multidomain formulation, in which the switching points appear as unknown parameters. Then, by utilizing Legendre‐Radau pseudospectral method, a nonlinear programming problem is derived which can be solved by the well‐developed parameter optimization algorithms. The main advantages of the present method are its superior accuracy and ability to capture the switching times. Accuracy and performance of the proposed method are examined by means of some numerical experiments. Copyright © 2016 John Wiley & Sons, Ltd.     

Deep eutectic solvent based homogeneous liquid–liquid extraction coupled with in‐syringe dispersive liquid–liquid microextraction performed in narrow tube; application in extraction and preconcentration of some herbicides from tea

A homogeneous liquid‐liquid extraction performed in narrow tube coupled to in–syringe‐dispersive liquid‐liquid microextraction based on deep eutectic solvent has been developed for the extraction of six herbicides from tea samples. In this method, sodium chloride as a separation agent is filled into the narrow tube and the tea sample is placed on top of the salt. Then a mixture of deionized water and deep eutectic solvent (water miscible) is passed through the tube. In this procedure, the deep eutectic solvent is realized as tiny droplets in contact with salt. By passing the droplets from the tea layer placed on the salt layer, the analytes are extracted into them. After collecting the solvent as separated layer, it is mixed with another deep eutectic solvent (choline chloride/butyric acid) and the mixture is dispersed into deionized water placed in a syringe. After adding acetonitrile to break up the cloudy state, the collected organic phase is injected into gas chromatography‐mass spectrometry. Under optimal conditions, limits of detection and quantification in the ranges of 2.6–8.4 and 9.7–29 ng/kg, respectively, were obtained. The extraction recoveries and enrichment factors in the ranges of 70–89% and 350–445 were obtained, respectively.     

Effects of Inorganic Nano-Additives on Properties and Performance of Polymeric Membranes in Water Treatment

Separation using selective polymeric membranes has been well-established as an energy-efficient and cost-effective technology in water treatment and many other applications involving aqueous solutions. However, limited chemical, thermal, and mechanical resistances besides their tendency to fouling and inadequate pure water flux may often restrict their applications. To this end, inorganic materials as additives have been demonstrated to be able to enhance chemical, thermal, and fouling membrane resistances, which demonstrate their great potential for developing novel membranes by using them as additives in polymer matrices. Considering the excellent characteristics of the nanosized particles, this study reviews the effects of inorganic nano-additives on properties and performance of polymer/nanoparticle composite membranes. It has been demonstrated that using nanomaterials in a polymer matrix could enhance the mechanical strength and stiffness, wettability, selectivity, water permeability, and antifouling characteristics of the host polymer.     

Extension of the Lasserre-Avrachenkov theorem on the integral of multilinear forms over simplices

The Lasserre-Avrachenkov theorem on integration of symmetric multilinear forms over simplices establishes a method (called LA) for integrating homogeneous polynomials over simplices. Although the computational complexity of LA is generally much higher than that of the other known methods (e.g. Grundmann-Moller formula), it is still useful in deriving closed-form expressions for the value of such integrals. However, LA cannot be directly applied for nonhomogeneous polynomials. It is shown in this paper that Lasserre-Avrachenkov theorem holds for a wider class of symmetric forms, to be called quasilinear forms. This extension can substantially facilitate derivation of a closed-form expression (not computation) for integral of some nonhomogeneous polynomials (such as ) over simplices.     

A General Method for Extracting Individual Coupling Constants from Crowded 1H NMR Spectra

Couplings between protons, whether scalar or dipolar, provide a wealth of structural information. Unfortunately, the high number of ¹H‐¹H couplings gives rise to complex multiplets and severe overlap in crowded spectra, greatly complicating their measurement. Many different methods exist for disentangling couplings, but none approaches optimum resolution. Here, we present a general new 2D J‐resolved method, PSYCHEDELIC, in which all homonuclear couplings are suppressed in F₂, and only the couplings to chosen spins appear, as simple doublets, in F₁. This approaches the theoretical limit for resolving ¹H‐¹H couplings, with close to natural linewidths and with only chemical shifts in F₂. With the same high sensitivity and spectral purity as the parent PSYCHE pure shift experiment, PSYCHEDELIC offers a robust method for chemists seeking to exploit couplings for structural, conformational, or stereochemical analyses.     

Efficient model order reduction for dynamic systems with local nonlinearities

In the nonlinear structural analysis, the nonlinear effects are commonly localized and the rest of the structure behaves in a linear manner. Considering this fact, this research work proposes a harmonic balance solution in order to determine the nonlinear response of the structures. The solution is simplified by using an exact dynamic reduction along with the modal expansion technique. This novel approach, which is applicable to both discrete and continuous systems, converts the system equations of motion in each harmonic to a small set of nonlinear algebraic equations. The full set of system equations is reduced to a discrete system with a few generalized degrees of freedom (DOFs) confined to the localized nonlinear regions. The resultant reduced order model is shown to be accurate enough for determining the periodic response. To demonstrate the capability of the proposed method, numerical case studies for continuous and discrete systems, including systems with internal resonance, have been studied and the outcomes are validated with benchmark studies. In addition, the method is applied in the identification process of an experimental test setup with unknown frictional support parameters, and the results are presented and discussed.