Unmasking Sensory Defects of Olive Oils Flavored with Basil and Oregano Using an Electronic Tongue-Chemometric Tool

Olive oil price and consumers’ preference depend on the commercial grade classification that can decrease if any sensory defect is perceived leading to an economic loss. Enriched oils, obtained by incorporating dried aromatic herbs, spices, or essential oils, which is a common practice in the Mediterranean region, are commercially available. This practice may conceal the fraudulent purpose of masking the perception of sensory defects. The detection of this type of fraud is a difficult task, requiring sensory analysis. Thus, in this study, extra-virgin and lampante olive oils, the latter classification being due to the perception of an intense winey-vinegary defect, were deliberately enriched with different amounts of basil-dried herbs and oregano-dried herbs. Sensory analysis showed that, depending on the aromatic herb and on the added amount (0.011–0.110 g herb per kg oil), the defect intensity could be masked leading to an erroneous classification of flavored lampante oils as flavored virgin oils. In contrast, the electronic tongue-chemometric approach could unmask the defect in flavored oils (predictive sensitivities: 70–78%) and semiquantitatively discriminate flavored oils according to the added levels of basil or oregano (predictive sensitivities: 93–100%). The electronic tongue approach showed satisfactory unmasking performance when compared with the sensory panel, and so, its future application as a quality control taste-sensor device for disclosing olive oil sensory defects masked by the incorporation of flavoring agents may be forseen.     

Electrospun microporous gelatin–polycaprolactone blend tubular scaffold as a potential vascular biomaterial

The work reported involved the fabrication of an electrospun tubular conduit of a gelatin and polycaprolactone (PCL) blend as an adventitia‐equivalent construct. Gelatin was included as the matrix for increased biocompatibility with the addition of PCL for durability. This is contrary to most of the literature available for biomaterials based on blends of gelatin and PCL where PCL is the major matrix. The work includes the assiduous selection of key electrospinning parameters to obtain smooth bead‐free fibres with a narrow distribution of pore size and fibre diameter. Few reports elucidate the optimization of all electrospinning parameters to fabricate tubular conduits with a focus on obtaining homogeneous pores and fibres. This stepwise investigation would be unique for the fabrication of gelatin–PCL electrospun tubular constructs. The fabricated microfibrous gelatin–PCL constructs had pores of size ca 50–100 μm reportedly conducive for cell infiltration. The measured value of surface roughness of 57.99 ± 17.4 nm is reported to be favourable for protein adhesion and cell adhesion. The elastic modulus was observed to be similar to that of the tunica adventitia of the native artery. Preliminary in vitro and in vivo biocompatibility tests suggest safe applicability as a biomaterial. Minimal cytotoxicity was observed using MTT assay. Subcutaneous implantation of the scaffold demonstrated acute inflammation which decreased by day 15. The findings of this study could enable the fabrication of smooth bead‐free microfibrous gelatin–PCL tubular construct as viable biomaterial which can be included in a bilayer or a trilayer scaffold for vascular tissue engineering. © 2019 Society of Chemical Industry     

Thulium and Ytterbium-Doped Titanium Oxide Thin Films Deposited by Ultrasonic Spray Pyrolysis

Thin films of thulium and ytterbium-doped titanium oxide were grown by metal-organic spray pyrolysis deposition from titanium(IV)oxide bis(acetylacetonate), thulium(III) tris(2,2,6,6-tetramethyl-3,5-heptanedionate) and ytterbium(III) tris(acetylacetonate). Deposition temperatures have been investigated from 300 to 600 °C. Films have been studied regarding their crystallinity and doping quality. Structural and composition characterisations of TiO₂:Tm,Yb were performed by electron microprobe, x-ray diffraction, and Fourier transform infrared spectroscopy. The deposition rate can reach 0.8 μm/h. The anatase phase of TiO₂ was obtained after synthesis at 400 °C or higher. Organic contamination at low deposition temperature is eliminated by annealing treatments.     

Viscosity properties of aqueous solution of poly(allylamine)-metal complexes

Poly(allylamine)-metal complexes with Co(II), Cu(II), and Ni(II) in conjunction with an ultrafiltration membrane were prepared. They were obtained varying the polymer/metal ion ratio and the pH (1, 3, 5, 7).     

Catalytic Epoxidation and Sulfoxidation Activity of a Dioxomolybdenum(VI) Complex Bearing a Chiral Tetradentate Oxazoline Ligand

A dioxomolybdenum(vi) complex bearing a tetradentate anionic N,O oxazoline ligand with four stereocenters has been studied as a catalyst in the liquid-phase epoxidation of 17 different aliphatic and aromatic olefins (including prochiral, racemate or pure enantiomers) using tert-butyl hydroperoxide as the oxidant. Epoxide selectivities of up to 100% and variable epoxide yields (3–100% within 24 h) were obtained. Although the complex generally exhibited low or no chiral induction ability, diastereoselectivity was significant in some cases (in the reaction of limonene, for example). Kinetic studies and recycling tests with the substrates cis-cyclooctene and trans-β-methylstyrene showed that the catalyst is stable and reusable, and recycling is facilitated by immobilization of the complex in a room temperature ionic liquid. Preliminary results show that the complex may have a broad substrate scope, not only for olefin epoxidation, but also for the dehydrogenation of alcohols to carbonyl compounds and the sulfoxidation of sulfides to sulfoxides.     

A novel process for the ethyl lactate synthesis in a simulated moving bed reactor (SMBR)

A novel approach for the synthesis of ethyl lactate using a simulated moving bed reactor was evaluated by experiments as well as by simulations. A mathematical model considering external and internal mass-transfer resistances and variable velocity due to change of liquid composition was developed to describe the dynamic behaviour of the SMBR and it was validated by the experiments performed; it was observed that the experimental results were well predicted by the model. The effect of operating parameters, as the feed composition, SMBR configuration and switching time on the SMBR performance parameters at the optimal operating points and/or reactive/separation regions was studied. It was shown that the SMBR is a very attractive technology for the production of ethyl lactate, since under appropriate conditions the lactic acid conversion can be driven to completion and productivity as high as and purity of 95% can be obtained.     

Polyelectrolyte adsorption study on polyethersulfone membrane during polymer-enhanced ultrafiltration by electrochemical impedance spectroscopy

Electrochemical impedance spectroscopy (EIS) was used to study the fouling produced due to the adsorption of poly(vinyl sulfonic acid) on polyethersulfone membrane during metal ion recovery by polymer-enhanced ultrafiltration (PEUF). A solution of PVSA (40 mM in monomeric unit and pH 3.0, 4.5, and 6.0) was placed in a ultrafiltration cell, and then a stream of metal ions (2.0 mM in Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, and Pb²⁺) was passed from reservoir to cell. Fouled membranes were studied by EIS at low and intermediate frequencies. Measurements of hydrodynamic permeability and ATR-FTIR spectra were also obtained. Different relaxation processes were observed with characteristic frequencies (f ₀) ~ 78 kHz and f ₀ ~ 3562 kHz for active layer and clean membrane, respectively, while the frequencies for the fouled membrane f ₀ = ~79.4 and f ₀ = ~2511.9 kHz (pH 3.0). The value of f ₀ could not be defined at pH 6.0. The relaxation times obtained were in the order of ×10⁻⁵ and ×10⁻³ s approximately for all cases. Our results suggest that relaxation mechanisms, at intermediate frequencies, can mainly be associated to polarization processes or to the migration of charge carriers.     

Contributing to Understand the Crosstalk between Brain and Periphery in Methylmercury Intoxication: Neurotoxicity and Extracellular Vesicles

Human exposure to methylmercury (MeHg) is currently high in regions such as the Amazon. Understanding the molecular changes associated with MeHg-induced neurotoxicity and the crosstalk with the periphery is essential to support early diagnoses. This work aimed to evaluate cellular and molecular changes associated with behavioral alterations in MeHg acute exposure and the possible changes in extracellular vesicles (EVs) number and S100β content. Adults male Wistar rats were orally treated with 5 mg/kg for four days. Behavioral performance, molecular and histological changes in the cerebellum, and plasma EVs were assessed. MeHg-intoxicated animals performed significantly worse in behavioral tests. MeHg increased the number of GFAP+ cells and GFAP and S100β mRNA expression in the cerebellum but no change in NeuN+ or IBA-1+ cells number was detected. The number of exosomes isolated from plasma were decreased by the metal. S100B mRNA was detected in circulating plasma EVs cargo in MeHg exposure. Though preliminary, our results suggest astrocytic reactivity is displaying a protective role once there was no neuronal death. Interestingly, the reduction in exosomes number could be a new mechanism associated with MeHg-induced neurotoxicity and plasma EVs could represent a source of future biomarkers in MeHg intoxication.     

CalDAG-GEFI Deficiency in a Family with Symptomatic Heterozygous and Homozygous Carriers of a Likely Pathogenic Variant in RASGRP2

RASGRP2 encodes the calcium and diacylglycerol (DAG)-regulated guanine nucleotide exchange factor I (CalDAG-GEFI) identified as a Rap1-activating molecule. Pathogenic variants previously identified in RASGRP2 allowed the characterization of CalDAG-GEFI deficiency as a non-syndromic, autosomal recessive platelet function disease. We report on the clinical manifestations and laboratory features of a Portuguese family with a likely pathogenic variant in RASGRP2 (c.999G>C leading to a p.Lys333Asn change in the CDC25 catalytic domain of CalDAG-GEFI) and discuss the contribution of this variant to the disease manifestations. Based on the study of this family with one homozygous patient and five heterozygous carriers and on a critical analysis of the literature, we challenge previous knowledge that CalDAG-GEFI deficiency only manifests in homozygous patients. Our data suggest that at least for the RASGRP2 variant reported herein, there is a phenotypic expression, albeit milder, in heterozygous carriers.     

(De)stabilization of Alpha-Synuclein Fibrillary Aggregation by Charged and Uncharged Surfactants

Parkinson’s disease (PD) is the second most common neurodegenerative disorder. An important hallmark of PD involves the pathological aggregation of proteins in structures known as Lewy bodies. The major component of these proteinaceous inclusions is alpha (α)-synuclein. In different conditions, α-synuclein can assume conformations rich in either α-helix or β-sheets. The mechanisms of α-synuclein misfolding, aggregation, and fibrillation remain unknown, but it is thought that β-sheet conformation of α-synuclein is responsible for its associated toxic mechanisms. To gain fundamental insights into the process of α-synuclein misfolding and aggregation, the secondary structure of this protein in the presence of charged and non-charged surfactant solutions was characterized. The selected surfactants were (anionic) sodium dodecyl sulphate (SDS), (cationic) cetyltrimethylammonium chloride (CTAC), and (uncharged) octyl β-D-glucopyranoside (OG). The effect of surfactants in α-synuclein misfolding was assessed by ultra-structural analyses, in vitro aggregation assays, and secondary structure analyses. The α-synuclein aggregation in the presence of negatively charged SDS suggests that SDS-monomer complexes stimulate the aggregation process. A reduction in the electrostatic repulsion between N- and C-terminal and in the hydrophobic interactions between the NAC (non-amyloid beta component) region and the C-terminal seems to be important to undergo aggregation. Fourier transform infrared spectroscopy (FTIR) measurements show that β-sheet structures comprise the assembly of the fibrils.