Application of liquid chromatography quadrupole time-of-flight mass spectrometry to the identification of acetamiprid transformation products generated under oxidative processes in different water matrices

This work allowed the identification of major transformation products (TPs) of acetamiprid (ACTM) during Fenton process. Acetamiprid is a chloronicotinoid insecticide widely used around the world for its characteristics (high insecticidal activity, good systemic properties, suitable field stability, etc.). The degradation of the parent molecule and the identification of the main TPs were evaluated in different water matrices (demineralized water and real agro-food industrial wastewater). TPs of acetamiprid generated by Fenton experiments were monitored and identified by liquid chromatography quadrupole time-of-flight tandem mass spectrometry (LC–QTOF–MS/MS). Up to 14 TPs were characterized based on the accurate mass of the molecular ion and fragment ions obtained in both full-scan and MS/MS modes. Most of them were eliminated after 75 min of treatment time in demineralized water. However, in real agro-food industrial wastewater, most of them were eliminated at 90 min of treatment time, demonstrating the influence of the matrix composition on the studied compound degradation.     

Nanocomposite Polymer Electrolytes of Sodium Alginate and Montmorillonite Clay

Nanocomposite polymer electrolytes (NPEs) were synthesized using sodium alginate (Alg) and either sodium (SCa-3-Na⁺)- or lithium (SCa-3-Li⁺)-modified montmorillonite clays. The samples were characterized by structural, optical, and electrical properties. SCa-3-Na⁺ and SCa-3-Li⁺ clays’ X-ray structural analyses revealed peaks at 2θ = 7.2° and 6.7° that corresponded to the interlamellar distances of 12.3 and 12.8 Å, respectively. Alg-based NPEs X-ray diffractograms showed exfoliated structures for samples with low clay percentages. The increase of clay content promoted the formation of intercalated structures. Electrochemical Impedance Spectroscopy revealed that Alg-based NPEs with 5 wt% of SCa-3-Na⁺ clay presented the highest conductivity of 1.96 × 10⁻² S/cm², and Alg with 10 wt% of SCa-3-Li⁺ showed conductivity of 1.30 × 10⁻² S/cm², both measured at 70 °C. From UV-Vis spectroscopy, it was possible to infer that increasing concentration of clay promoted a decrease of the samples’ transmittance and, consequently, an increase of their reflectance.     

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.     

Natural Polymers-Based Materials: A Contribution to a Greener Future

Natural polymers have emerged as promising candidates for the sustainable development of materials in areas ranging from food packaging and biomedicine to energy storage and electronics. In tandem, there is a growing interest in the design of advanced materials devised from naturally abundant and renewable feedstocks, in alignment with the principles of Green Chemistry and the 2030 Agenda for Sustainable Development. This review aims to highlight some examples of the research efforts conducted at the Research Team BioPol4fun, Innovation in BioPolymer-based Functional Materials and Bioactive Compounds, from the Portuguese Associate Laboratory CICECO–Aveiro Institute of Materials at the University of Aveiro, regarding the exploitation of natural polymers (and derivatives thereof) for the development of distinct sustainable biobased materials. In particular, focus will be given to the use of polysaccharides (cellulose, chitosan, pullulan, hyaluronic acid, fucoidan, alginate, and agar) and proteins (lysozyme and gelatin) for the assembly of composites, coatings, films, membranes, patches, nanosystems, and microneedles using environmentally friendly strategies, and to address their main domains of application.     

Healthy Properties of a New Formulation of Pomegranate-Peel Extract in Mice Suffering from Experimental Autoimmune Encephalomyelitis

A new formulation of a pomegranate-peel extract (PEm) obtained by PUAE (Pulsed Ultrasound-Assisted Extraction) and titrated in both ellagic acid (EA) and punicalagin is proposed, characterized and then analyzed for potential health properties in mice suffering from the experimental autoimmune encephalomyelitis (EAE). PEm effects were compared to those elicited by a formulation containing EA (EAm). Control and EAE mice were chronically administered EAm and Pem dissolved in the drinking water, starting from the day 10 post-immunization (d.p.i.), with a “therapeutic” protocol to deliver daily 50 mg/kg of EA. Treated EAE mice did not limit their daily access to the beverage, nor did they show changes in body weight, but they displayed a significant amelioration of “in vivo” clinical symptoms. “Ex vivo” histochemical analysis showed that spinal-cord demyelination and inflammation in PEm and EAm-treated EAE mice at 23 ± 1 d.p.i. were comparable to those in the untreated EAE animals, while microglia activation (measured as Ionized Calcium Binding Adaptor 1, Iba1 staining) and astrocytosis (quantified as glial fibrillar acid protein, GFAP immunopositivity) significantly recovered, particularly in the gray matter. EAm and PEm displayed comparable efficiencies in controlling the spinal pathological cellular hallmarks in EAE mice, and this would support their delivery as dietary supplementation in patients suffering from multiple sclerosis (MS).     

Effects of Regioisomerism on the Antiproliferative Activity of Hydroxystearic Acids on Human Cancer Cell Lines

A series of regioisomers of the hydroxystearic acid (HSA) was prepared, and the effect of the position of the hydroxyl group along the chain on a panel of human cancer cell lines was investigated. Among the various regioisomers, those carrying the hydroxyl at positions 5, 7, and 9 had growth inhibitor activity against various human tumor cell lines, including CaCo-2, HT29, HeLa, MCF7, PC3, and NLF cells. 10-HSA and 11-HSA showed a very weak effect. 8-HSA did not show inhibitory activity in all cell lines. The biological role of 7-HSA and 9-HSA is widely recognized, while little is known about the effects of 5-HSA. Therefore, the biological effects of 5-HSA in HeLa, HT29, MCF7, and NLF cell lines were investigated using the Livecyte’s ptychography technology, which allows correlating changes in proliferation, motility, and morphology as a function of treatment at the same time. 5-HSA not only reduces cell proliferation but also induces changes in cell displacement, directionality, and speed. It is important to characterize the biological effects of 5-HSA, this molecule being an important component of fatty acyl esters of hydroxy fatty acids (FAHFA), a class of endogenous mammalian lipids with noticeable anti-diabetic and anti-inflammatory effects.     

Multiplexed therapeutic drug monitoring of antipsychotics in dried plasma spots by LC‐MS/MS

In this work, a convenient method for the therapeutic monitoring of seven common antipsychotic drugs in “dried plasma spot” samples has been developed. It is based on the liquid chromatography tandem mass spectrometry technique, operating in multiple reaction monitoring mode, and a straightforward procedure for the simultaneous extraction of all antipsychotics in a single step, with high extraction yield. The method was fully validated with proper accuracy, precision, selectivity and sensitivity, for all the drugs. Limits of quantification were 0.12, 1.09, 1.46, 1.47, 5.70, 1.32, 1.33 µg/L for haloperidol, aripiprazole, olanzapine, quetiapine, clozapine, risperidone, and paliperidone, respectively. Accuracy, intra‐ and interday precision values were <10% for all drugs at all concentration levels examined. The method was tested in the analysis of 30 plasma samples from real patients for each drug. The proposed analytical approach, by combining practical and logistical advantages of microsampling with liquid chromatography tandem mass spectrometry analytical performance, could offer an ideal strategy for accurate and timely therapeutic drug monitoring of antipsychotic drugs in most clinical settings, even in remote centers and/or in out‐patient settings, bringing so many potential improvements in psychiatric patient care.     

Radon levels in underground workplaces – results of a nationwide survey in Italy

In Italy an extensive survey has been carried out with the aim to evaluate annual average radon concentration in underground workplaces.The survey covered 933 underground rooms located in 311 bank workplaces spread throughout in all Italian regions; at this scope the sampling was stratified random in order to be representative on national scale. The annual radon concentration was estimated by using passive radon dosemeters (NRPB/SSI type holder and CR-39 as detector): the devices were exposed for a period of about 3 months and 4 cycles were performed to cover a solar year. The radon levels in underground workplaces ranged from 27 to 4851 Bq/m³ with an overall mean value of 153 Bq/m³. As expected, radon distribution is not uniform throughout Italy: in several regions high radon annual averages have been found, confirming previous surveys.The analysis of data shows a high variability among regions and intra-region but low spread among rooms belonging to the same workplace.About 5% of underground workplaces displayed radon concentration exceeding 400 Bq/m³, and the 4.4% exceeds 500 Bq/m³, the national action level for the exposure to natural radioactivity in workplaces.