Enhanced electrochemical detection of quercetin by Natural Deep Eutectic Solvents

New trends in analytical chemistry encourage the development of smart techniques and methods aligned with Green Chemistry. In this sense, Natural Deep Eutectic Solvents represents an excellent opportunity as a new generation of green solvents. In this work a new application for them has been proposed and demonstrated. These solvents were synthesized by combinations of inexpensive and natural components like, Glucose, Fructose, Citric acid and Lactic acid. The different natural solvents were easily prepared and added to buffer solution in different concentrations, allowing the enhancement of electrochemical detection of an important representative antioxidant like quercetin (QR) with improved signal up to 380%. QR is a ubiquitous flavonoid widespread in plants and food of plant origin. The proposed method using phosphate buffer with a eutectic mixture of Citric acid, Glucose and water in combination with carbon screen printed electrodes exhibited a good analytical performance. Detection and quantification limits were of 7.97 and 26.3 nM respectively; and repeatability with %RSDs of 1.41 and 7.49 for peak potential and intensity respectively. In addition, it has proved to be faster, greener and cheaper than other sensors and chromatographic methods available with the additional advantage of being completely portable. Furthermore, the obtained results demonstrated that the proposed method is able for the determination of QR in complex food samples.     

Voltammetric determination of linuron at a carbon-paste electrode modified with sepiolite

The determination of linuron by differential pulse voltammetry with a carbon-paste electrode modified with 20% w/w sepiolite has been studied. The linuron is preconcentrated under open-circuit conditions at pH 2.0. With 0.01M potassium nitrate at pH 1.7 in the measurement cell, a sweep rate of 30 mV/sec and a pulse amplitude of 100 mV, an oxidation wave with a peak potential of 1.2 V is obtained. Under these conditions, determination limits of 75 ng/ml have been obtained, with a relative error of +2.8% and a relative standard deviation of 8.0%. The method has been applied to the direct determination of linuron in river water with no previous separation of the pesticide. Determination in sea-water is not possible, as chloride interferes at high concentration.     

A slender-body micromechanical model for viscoelasticity of magnetic colloids: comparison with preliminary experimental data

The storage modulus, G', together with the yield stress, is an essential quantity characterizing the rheological properties of magnetic field-responsive suspensions (magnetorheological fluids or MRF). In this work, we present both experimental and theoretical results on the viscoelastic properties of MRFs. Two MRFs are used: In one the solid phase consists of cobalt ferrite particles + silica gel, with silicone oil as liquid phase. The second system is formed by carbonyl iron + silica gel also dispersed in silicone oil. The cobalt ferrite particles are synthesized as monodisperse colloidal spheres with an average diameter of 850 nm. We describe a new model based on the slender-body approach for hydrodynamic interactions. The predictions of the model are compared to preliminary experimental G' data obtained in a controlled stress plate-plate rheometer. It is found that the model gives the correct order of magnitude for the highest fields in iron suspensions, but underestimates the experimental results obtained in ferrite ones. In the case of high permeability materials such as carbonyl iron, by the inclusion of high-order multipolar interactions and saturation effects we also predict the order of magnitude of the experimental results. When dealing with low permeability cobalt ferrite based MRFs, other effects, such as remanence (at low fields) and saturation (at high fields), must be considered.     

Fractional integral sliding modes for robust tracking of nonlinear systems

Memory and heritage of differintegral operators require knowledge of the error manifold derivative at the initial time to sustain a sliding motion for any initial condition. Moreover, when the system is subject to (unknown) disturbances, such initial condition is unknown; thus, the enforcement of an integral sliding motion has been elusive with a chatter-less controller. In this paper, a novel fractional-order integral sliding mode (FISM) is proposed to maintain an invariant sliding mode due to an exact estimation of disturbances at first step. Our scheme is continuous after initial condition, avoiding chattering effects thanks to the topological properties of differintegral operators. In contrast to other FISM approaches, the proposed scheme induces a fractional-order reaching dynamics of order \((1+\nu )\in (1,2)\) to enforce an integral sliding mode for any initial condition, even in the presence of Hölder (continuous but not necessarily differentiable) disturbances and model uncertainties. Simulations show the reliability of the proposed scheme.     

A Narrative Review of the Current Knowledge on Fruit Active Aroma Using Gas Chromatography-Olfactometry (GC-O) Analysis

Fruit aroma, a mixture of chemical compounds with odor, is a strong attractant derived from a complex mixture of different amounts and intensities (threshold) of chemical compounds found in fruits. The odor-producing compounds of fruit aroma are derived from carbohydrates, lipids, phenolic compounds, and mono- and sesquiterpenes, among others. The identification of compounds responsible for fruit aroma is usually conducted using gas chromatography coupled with olfactometry (GC-O). This technique separates the chemical compounds from the aroma of foods using a chromatographic column and divides the resultant outflow between the physical detector and a testing outlet (sniffing port). Trained judges describe the perceived odor in terms of the intensity of the odor zones perceived according to their training method. Moreover, the use of GC-O coupled with a mass detector (GC-MS-O) allows for the retrieval of chemical information such as identification and quantification of compounds, which can be correlated to sensory information. This review aimed to demonstrate the application of GC-MS-O in the identification of precursor compounds in fruit aroma, considering important factors for the application, main results, and most recent advances in this field.     

Magnetic and Luminescence Properties of 8-Coordinate Holmium(III) Complexes Containing 4,4,4-Trifluoro-1-Phenyl- and 1-(Naphthalen-2-yl)-1,3-Butanedionates

A new series of mononuclear Ho³⁺ complexes derived from the β-diketonate anions: 4,4,4-trifluoro-1-phenyl-1,3-butanedioneate (btfa⁻) and 4,4,4-trifuoro-1-(naphthalen-2-yl)-1,3-butanedionate (ntfa⁻) have been synthesized, [Ho(btfa)₃(H₂O)₂] (1a), [Ho(ntfa)₃(MeOH)₂] (1b), (1), [Ho(btfa)₃(phen)] (2), [Ho(btfa)₃(bipy)] (3), [Ho(btfa)₃(di-^tbubipy)] (4), [Ho(ntfa)₃(Me₂bipy)] (5), and [Ho(ntfa)₃(bipy)] (6), where phen is 1,10-phenantroline, bipy is 2,2′-bipyridyl, di-^tbubipy is 4,4′-di-tert-butyl-2,2′-bipyridyl, and Me₂bipy is 4,4′-dimethyl-2,2′-bipyridyl. These compounds have been characterized by elemental microanalysis and infrared spectroscopy as well as single-crystal X-ray difraction for 2–6. The central Ho³⁺ ions in these compounds display coordination number 8. The luminescence-emission properties of the pyridyl adducts 2–6 display a strong characteristic band in the visible region at 661 nm and a series of bands in the NIR region (excitation wavelengths (λ_ex) of 367 nm for 2–4 and 380 nm for 5 and 6). The magnetic properties of the complexes revealed magnetically uncoupled Ho³⁺ compounds with no field-induced, single-molecule magnet (SMMs).     

Factors That Affect the Accumulation of Strecker Aldehydes in Standardized Wines: The Importance of pH in Oxidation

Strecker aldehydes (SA) can be formed in wine from the degradation of Strecker and, to a lesser degree, via the oxidation of higher alcohols. The objective of this article is to assess the magnitude of the differences introduced by wine compositional factors other than amino acids and Fe, in the accumulation of SA during oxidation. Eight red, two rosé and two white wines were oxidized. The accumulation of SA was analyzed. Whites and rosés presented negative accumulations for isobutyraldehyde, and in general, these wines accumulated smaller concentrations of the other SA than red wines. Only methional and phenylacetaldehyde were accumulated in all of the wines during oxidation. 2-methylbutanal and 3-methylbutanal were accumulated in 9 out of the 12 wines, whereas isobutyraldehyde was accumulated only in 5 out of the 12. 2-methylbutanal was, on average, the least accumulated aldehyde. Methional was the aldehyde formed most homogenously. Most of the observed differences can be attributed to three factors: the pH, oxidation time and native levels of Strecker aldehydes. The influence of pH was particularly intense in the cases of phenylacetaldehyde and methional. An independent test using synthetic wines with Strecker amino acids and 4-methylcatechol with different pHs (4.2, 3.5 and 2.8) was carried out in order to verify the higher pH value, the greater accumulation in SA after oxidation process. The results strongly suggest the important role played by pH in the accumulation of SA in wine oxidation.