Novel Fast Chromatography-Tandem Mass Spectrometric Quantitative Approach for the Determination of Plant-Extracted Phytosterols and Tocopherols

Phytosterols and tocopherols are commonly used in food and pharmaceutical industries for their health benefits. Current analysis methods rely on conventional liquid chromatography, using an analytical column, which can be tedious and time consuming. However, simple, and fast analytical methods can facilitate their qualitative and quantitative analysis. In this study, a fast chromatography-tandem mass spectrometric (FC-MS/MS) method was developed and validated for the quantitative analysis of phytosterols and tocopherols. Omitting chromatography by employing flow injection analysis—mass spectrometry (FIA-MS) failed in the quantification of target analytes due to analyte-to-analyte interferences from phytosterols. These interferences arise from their ambiguous MS fingerprints that would lead to false identification and inaccurate quantification. Therefore, a C18 guard column with a 1.9 µm particle size was employed for FC-MS/MS under isocratic elution using acetonitrile/methanol (99:1 v/v) at a flow rate of 600 µL/min. Analyte-to-analyte interferences were identified and eliminated. The false peaks could then be easily identified due to chromatographic separation. In addition, two internal standards were evaluated, namely cholestanol and deuterated cholesterol. Both internal standards contributed to the observed analyte-to-analyte interferences; however, adequate shift in the retention time for deuterated cholesterol eliminated its interferences and allowed for an accurate quantification. The method is fast (1.3 min) compared to published methods and can distinguish false peaks observed in FIA-MS. Seven analytes were quantified simultaneously, namely brassicasterol, campesterol, stigmasterol, β-sitosterol, α-tocopherol, δ-tocopherol, and γ-tocopherol. The method was successfully applied in the quantitative analysis of phytosterols and tocopherols present in the unsaponifiable matter of canola oil deodorizer distillate (CODD). β-sitosterol and γ-tocopherol were the most abundant phytosterols and tocopherols, respectively.     

Mixing of electronic states in pentacene adsorption on copper

By combining experimental and theoretical approaches, we study the adsorption of pentacene on copper as a model for the coupling between aromatic molecules and metal surfaces. Our results for the interface electronic structure are not compatible with a purely physisorption picture, which is conventionally employed for such systems. Nay, we demonstrate electronic mixing between molecular orbitals and metal electronic states.     

Dynamical phases of the Hindmarsh-Rose neuronal model: studies of the transition from bursting to spiking chaos

The dynamical phases of the Hindmarsh-Rose neuronal model are analyzed in detail by varying the external current I. For increasing current values, the model exhibits a peculiar cascade of nonchaotic and chaotic period-adding bifurcations leading the system from the silent regime to a chaotic state dominated by bursting events. At higher I-values, this phase is substituted by a regime of continuous chaotic spiking and finally via an inverse period doubling cascade the system returns to silence. The analysis is focused on the transition between the two chaotic phases displayed by the model: one dominated by spiking dynamics and the other by bursts. At the transition an abrupt shrinking of the attractor size associated with a sharp peak in the maximal Lyapunov exponent is observable. However, the transition appears to be continuous and smoothed out over a finite current interval, where bursts and spikes coexist. The beginning of the transition (from the bursting side) is signaled from a structural modification in the interspike interval return map. This change in the map shape is associated with the disappearance of the family of solutions responsible for the onset of the bursting chaos. The successive passage from bursting to spiking chaos is associated with a progressive pruning of unstable long-lasting bursts.     

Total Synthesis of a Partial Structure from Arabinogalactan and Its Application for Allergy Prevention

Arabinogalactan, a microheterogeneous polysaccharide occurring in plants, is known for its allergy-protective activity, which could potentially be used for preventive allergy treatment. New treatment options are highly desirable, especially in a preventive manner, due to the constant rise of atopic diseases worldwide. The structural origin of the allergy-protective activity of arabinogalactan is, however, still unclear and isolation of the polysaccharide is not feasible for pharmaceutical applications due to a variation of the activity of the natural product and contaminations with endotoxins. Therefore, a pentasaccharide partial structure was selected for total synthesis and subsequently coupled to a carrier protein to form a neoglycoconjugate. The allergy-protective activity of arabinogalactan could be reproduced with the partial structure in subsequent in vivo experiments. This is the first example of a successful simplification of arabinogalactan with a single partial structure while retaining its allergy-preventive potential.     

Synthesis and Characterization of Flexible Hydrogel Electrodes for Electrochemical Impedance Measurements of Protective Coatings on Metal Sculptures

A novel conductive anionic hydrogel was synthesized for use as a solid electrolyte for electrochemical impedance spectroscopy (EIS) characterization of the barrier properties of protective coatings on outdoor metalworks, such as bronze sculptures. The AMPS‐co‐PAA hydrogel was soaked in a variety of aqueous salt solutions and characterized by swelling capacity and conductivity in order to determine the most appropriate gel/liquid electrolyte combination for use on culturally significant objects. K₂PIPES‐equilibrated hydrogels were selected as the preferred electrodes for this particular application and were used to measure the impedance of a coated substrate, yielding spectra similar to those from standard liquid cells.     

Terroir Effect on the Phenolic Composition and Chromatic Characteristics of Mencía/Jaen Monovarietal Wines: Bierzo D.O. (Spain) and Dão D.O. (Portugal)

‘Mencía’/‘Jaen’ it’s an important red grape variety, exclusive of the Iberian Peninsula, used in wine production namely in Bierzo D.O. and Dão D.O., respectively. This work evaluates the effect of the two different “terroirs” on the phenolic composition and chromatic characteristics of ‘Mencía’/‘Jaen’ monovarietal wines produced at an industrial scale in the same vintage. Using Principal Component Analysis (PCA), Partial Least Squares-Discrimination Analysis (PLS-DA), and Orthogonal PLS-DA (OPLS-DA) it was found that peonidin-3-coumaroylglucoside, petunidin-3-glucoside, malvidin-3-coumaroylglucoside, peonidin-3-glucoside, malvidin-3-acetylglucoside, malvidin-3-glucoside, and ferulic acid were the phenolic compounds with the highest differences between the two regions. PLS regression allowed to correlate the differences in lightness (L*) and redness (a*) of wines from ‘Jaen’ and ‘Mencía’ to differences in colored anthocyanins, polymeric pigments, total pigments, total anthocyanins, cyanidin-3-acetylglucoside, delphinidin-3-acetylglucoside, delphinidin-3-glucoside, peonidin-3-coumaroylglucoside, petunidin-3-glucoside and malvidin-3-glucoside in wines, and the colorless ferulic, caffeic, and coutaric acids, and ethyl caffeate. The wines a* values were more affected by colored anthocyanins, ferulic acid, total anthocyanins, delphinidin-3-acetylglucoside, delphinidin-3-glucoside and petunidin-3-acetylglucoside, and catechin. The positive influence of ferulic acid in the a* values and ferulic, caffeic, coutaric acids, and ethyl caffeate on the L* values can be due to the co-pigmentation phenomena. The higher dryness and lower temperatures during the September nights in this vintage might explain the differences observed in the anthocyanin content and chromatic characteristics of the wines.     

Chemo‐ and Magnetotaxis of Self‐Propelled Light‐Emitting Chemo‐electronic Swimmers

Miniaturized autonomous chemo‐electronic swimmers, based on the coupling of spontaneous oxidation and reduction reactions at the two poles of light‐emitting diodes (LEDs), are presented as chemotactic and magnetotactic devices. In homogeneous aqueous media, random motion caused by a bubble‐induced propulsion mechanism is observed. However, in an inhomogeneous environment, the self‐propelled devices exhibit positive chemotactic behavior, propelling themselves along a pH or ionic strength gradient (?pH and ?I, respectively) in order to reach a thermodynamically higher active state. In addition, the intrinsic permanent magnetic moment of the LED allows self‐orientation in the terrestrial magnetic field or following other external magnetic perturbations, which enables a directional motion control coupled with light emission. The interplay between chemotaxis and magnetotaxis allows fine‐tuning of the dynamic behavior of these swimmers.     

Remote Actuation of a Light-Emitting Device Based on Magnetic Stirring and Wireless Electrochemistry

We propose a straightforward access to a rotating light-emitting device powered by wireless electrochemistry. A magnetic stirrer is used to rotate a light-emitting diode (LED) due to the intrinsic magnetic properties of the tips that contain iron. At the same time, the LED is submitted to an electric field and acts as a bipolar electrode. The electrochemical processes that are coupled on both extremities of the LED drive an electron flow across the device, resulting in light emission. The variation of the LED alignment in time enables an alternating light emission that is directly controlled by the rotation rate. The stirring also enables a continuous mixing of the electrolyte that improves the stability of the output signal. Finally, the LED brightness can readily reveal a change of chemical composition in the electrolyte solution.