Sensitive Determination of 17β-Estradiol using a Magneto Sensor Based on Magnetic Molecularly Imprinted Polymer

The analysis of 17β-estradiol with high sensitivity and selectivity is extremely relevant to control the impacts that this compound can cause on health and the environment. Thus, we describe the development and application of a magneto carbon paste electrode based on magnetic molecularly imprinted polymer (MCPE-MMIP) for determination of 17β-estradiol. The analyte adsorbed on the MMIP was immobilized on the electrode surface by magnetic capture. The morphological and structural characterization of the obtained MMIP suggests that the material was effectively synthesized. MCPE-MMIP showed an improvement in the sensitivity for 17β-estradiol detection when compared to electrode configurations in the absence of this material. The optimum conditions (0.10 mol L⁻¹ phosphate buffer pH 7.0) were reached by differential pulse adsorptive stripping voltammetry (DPAdSV), in which the method presented linearity ranged from 0.06 to 175 μmol L⁻¹ with limits of detection and quantification of 0.02 and 0.06 μmol L⁻¹, respectively. The proposed sensor was applied effectively in the analysis of 17β-estradiol in river water and raw milk samples, exhibiting excellent recovery values (between 96.20 and 104 %), which were confirmed by HPLC analysis.     

Giant spin splitting through surface alloying

The long-range ordered surface alloy Bi/Ag(111) is found to exhibit a giant spin splitting of its surface electronic structure due to spin-orbit coupling, as is determined by angle-resolved photoelectron spectroscopy. First-principles electronic structure calculations fully confirm the experimental findings. The effect is brought about by a strong in-plane gradient of the crystal potential in the surface layer, in interplay with the structural asymmetry due to the surface-potential barrier. As a result, the spin polarization of the surface states is considerably rotated out of the surface plane.     

Building symmetric polynomials to fit a potential energy surface: application to an A_2B_2 molecule

We present a method to build potential energy surfaces with the correct permutational symmetry of identical atoms. It is explained and applied to an A $_2$ B $_2$ molecular system. This method allows us to use different reference geometries, which are often needed in large molecules.     

Online Monitoring of Electrochemical Carbon Corrosion in Alkaline Electrolytes by Differential Electrochemical Mass Spectrometry

Carbon corrosion at high anodic potentials is a major source of instability, especially in acidic electrolytes and impairs the long‐term functionality of electrodes. In‐depth investigation of carbon corrosion in alkaline environment by means of differential electrochemical mass spectrometry (DEMS) is prevented by the conversion of CO₂ into CO₃^2?. We report the adaptation of a DEMS system for online CO₂ detection as the product of carbon corrosion in alkaline electrolytes. A new cell design allows for in situ acidification of the electrolyte to release initially dissolved CO₃^2? as CO₂ in front of the DEMS membrane and its subsequent detection by mass spectrometry. DEMS studies of a carbon‐supported nickel boride (Ni_xB/C) catalyst and Vulcan XC 72 at high anodic potentials suggest protection of carbon in the presence of highly active oxygen evolution electrocatalysts. Most importantly, carbon corrosion is decreased in alkaline solution.     

Parallel Homochiral and Anti‐Parallel Heterochiral Hydrogen‐Bonding Interfaces in Multi‐Helical Abiotic Foldamers

A hydrogen‐bonding interface between helical aromatic oligoamide foldamers has been designed to promote the folding of a helix‐turn‐helix motif with a head‐to‐tail arrangement of two helices of opposite handedness. This design complements an earlier helix‐turn‐helix motif with a head‐to‐head arrangement of two helices of identical handedness interface. The two motifs were shown to have comparable stability and were combined in a unimolecular tetra‐helix fold constituting the largest abiotic tertiary structure to date.     

From a Medicinal Mushroom Blend a Direct Anticancer Effect on Triple-Negative Breast Cancer: A Preclinical Study on Lung Metastases

Bioactive metabolites isolated from medicinal mushrooms (MM) used as supportive treatment in conventional oncology have recently gained interest. Acting as anticancer agents, they interfere with tumor cells and microenvironment (TME), disturbing cancer development/progression. Nonetheless, their action mechanisms still need to be elucidated. Recently, using a 4T1 triple-negative mouse BC model, we demonstrated that supplementation with Micotherapy U-Care, a MM blend, produced a striking reduction of lung metastases density/number, paralleled by decreased inflammation and oxidative stress both in TME and metastases, together with QoL amelioration. We hypothesized that these effects could be due to either a direct anticancer effect and/or to a secondary/indirect impact of Micotherapy U-Care on systemic inflammation/immunomodulation. To address this question, we presently focused on apoptosis/proliferation, investigating specific molecules, i.e., PARP1, p53, BAX, Bcl2, and PCNA, whose critical role in BC is well recognized. We revealed that Micotherapy U-Care is effective to influence balance between cell death and proliferation, which appeared strictly interconnected and inversely related (p53/Bax vs. Bcl2/PARP1/PCNA expression trends). MM blend displayed a direct effect, with different efficacy extent on cancer cells and TME, forcing tumor cells to apoptosis. Yet again, this study supports the potential of MM extracts, as adjuvant supplement in the TNBC management.     

Laquinimod Modulates Human Astrocyte Function and Dampens Astrocyte-Induced Neurotoxicity during Inflammation

Astrocytes greatly participate to inflammatory and neurotoxic reactions occurring in neurodegenerative diseases and are valuable pharmacological targets to support neuroprotection. Here we used human astrocytes generated from reprogrammed fibroblasts as a cellular model to study the effect of the compound Laquinimod and its active metabolite de-Laquinimod on astrocyte functions and the astrocyte–neuron interaction. We show that human iAstrocytes expressed the receptor for the inflammatory mediator IL1 and responded to it via nuclear translocation of NFκB, an event that did not occur if cells were treated with Laquinimod, indicating a direct anti-inflammatory activity of the drug on the human astrocyte. Similarly, while exposure to IL1 downregulated glial glutamate transporters GLAST and GLT1, treatment with Laquinimod supported maintenance of physiological levels of these proteins despite the inflammatory milieu. Laquinimod also induced nuclear translocation of the aryl hydrocarbon receptor (AHR), suggesting that drug action was mediated by activation of the AHR pathway. However, the drug was effective despite AHR inhibition via CH223191, indicating that AHR signaling in the astrocyte is dispensable for drug responses. Finally, in vitro experiments with rat spinal neurons showed that laquinimod did not exert neuroprotection directly on the neuron but dampened astrocyte-induced neurodegeneration. Our findings indicate that fibroblast-derived human astrocytes represent a suitable model to study astrocyte–neuron crosstalk and demonstrate indirect, partial neuroprotective efficacy for laquinimod.     

Mediterranean diet in a Sicilian student population. Second part: breakfast and its nutritional profile

Abstract

Breakfast habits affect the nutritional status and health of people, in particular children and adolescents. This is the second part a previous study about the adherence to the Mediterranean diet in a Sicilian (Italy) student population. The investigation analysed both normal weight and overweight subjects in order to understand how eating habits, number of meals and daily calorie intakes could affect their body mass indexes (BMI). The aim of this second part was to analyse the breakfast nutritional profiles of this student population. The results highlighted that breakfast was regularly consumed by a percentage ranging from a maximum of 84% (in normal subjects) to a minimum value of 57.4% (in overweight/obese students). Milk, yoghurt, sugar, bread/rusk and tea contributed as main foods to the breakfast composition. The results highlighted that subjects who consumed breakfast showed lower BMI values with significant differences between normal and overweight/obese students.     

Chemometric Optimization of Biologically Active Compounds Extraction from Grape Marc: Composition and Antimicrobial Activity

The article focuses on the optimization of the extraction process of biologically active compounds (BAC) from grape marc—a by-product of the wine industry. The influence of temperature, specifically 30 °C, 45 °C and 65 °C, and ethanol concentration in solutions, specifically 0–96% (v/v) on the extraction yield of polyphenols, flavonoids, tannins and anthocyanins, were investigated. The composition of individual polyphenols, anthocyanins and organic acids, antioxidant activity (DPPH and ABTS) and CIELab chromatic characteristics of the grape marc extracts (GME), were characterized. The microbiostatic and microbicidal effects in direct contact of GME with pathogenic microorganisms, Bacillus subtilis, Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, were determined in vitro. The influence of extraction parameters on the total polyphenol content (TPC), total flavonoid content (TFC), tannin content (TC), total anthocyanin content (TAC) and their interdependencies were studied using information analysis. A mathematical model was developed on cubic spline functions. The analysis of individual compounds showed the presence of a wide range of flavonoids (procyanidin B2, procyanidin B1, hyperoside and quercetin), flavones (catechin), hydroxybenzoic acid derivatives (gallic, protocatechuic, p-hydroxybenzoic acids, m-hydroxybenzoic acid, syringic acid), hydroxycinic acid derivatives and ferulic acid methyl ester. The malvidol-3-glucoside was the main anthocyanin identified in the extract. A high amount of tartaric acid was also found. GME showed significant antimicrobial activity against Gram-positive bacteria and lower activity against Gram-negative bacteria.     

Glucose/Ribitol Dehydrogenase and 16.9 kDa Class I Heat Shock Protein 1 as Novel Wheat Allergens in Baker’s Respiratory Allergy

Wheat allergens are responsible for symptoms in 60–70% of bakers with work-related allergy, and knowledge, at the molecular level, of this disorder is progressively accumulating. The aim of the present study is to investigate the panel of wheat IgE positivity in allergic Italian bakers, evaluating a possible contribution of novel wheat allergens included in the water/salt soluble fraction. The water/salt-soluble wheat flour proteins from the Italian wheat cultivar Bolero were separated by using 1-DE and 2-DE gel electrophoresis. IgE-binding proteins were detected using the pooled sera of 26 wheat allergic bakers by immunoblotting and directly recognized in Coomassie stained gel. After a preparative electrophoretic step, two enriched fractions were furtherly separated in 2-DE allowing for detection, by Coomassie, of three different proteins in the range of 21–27 kDa that were recognized by the pooled baker’s IgE. Recovered spots were analyzed by nanoHPLC Chip tandem mass spectrometry (MS/MS). The immunodetected spots in 2D were subjected to mass spectrometry (MS) analysis identifying two new allergenic proteins: a glucose/ribitol dehydrogenase and a 16.9 kDa class I heat shock protein 1. Mass spectrometer testing of flour proteins of the wheat cultivars utilized by allergic bakers improves the identification of until now unknown occupational wheat allergens.