Phytochemicals with Added Value from Morella and Myrica Species

Terrestrial plants, due to their sessile nature, are highly exposed to environmental pressure and therefore need to produce very effective molecules that enable them to survive all the threats. Myrica and Morella (Myricaceae) are taxonomically close genera, which include species of trees or shrubs with edible fruits that exhibit relevant uses in traditional medicine. For instance, in Chinese or Japanese folk medicine, they are used to treat diarrhea, digestive problems, headache, burns, and skin diseases. A wide array of compounds isolated from different parts of Myrica and/or Morella species possess several biological activities, like anticancer, antidiabetic, anti-obesity, and cardio-/neuro-/hepatoprotective activities, both in vitro and in vivo, with myricanol, myricitrin, quercitrin, and betulin being the most promising. There are still many other compounds isolated from both genera whose biological activities have not been evaluated, which represents an excellent opportunity to discover new applications for those compounds and valorize Morella/Myrica species.This research was funded by FCT-Fundação para a Ciência e a Tecnologia, supporting G.P.R.'s grant (SFRH/BD/144446/2019) as well by FCT-Fundação para a Ciência e Tecnologia, the European Union, QREN, FEDER, and COMPETE, through funding the cE3c center (UIDB/00329/2020) and the LAQV-REQUIMTE (UIDB/50006/2020). Funded by RTI2018-094356-B-C21 Spanish MINECO project, co-funded by European Regional Development Fund (FEDER).info:eu-repo/semantics/publishedVersio

Perfluoropolyethers: Development of an All-Atom Force Field for Molecular Simulations and Validation with New Experimental Vapor Pressures and Liquid Densities

A force field for perfluoropolyethers (PFPEs) based on the general optimized potentials for liquid simulations all-atom (OPLS-AA) force field has been derived in conjunction with experiments and ab initio quantum mechanical calculations. Vapor pressures and densities of two liquid PFPEs, perfluorodiglyme (CF3−O−(CF2−CF2−O)2−CF3) and perfluorotriglyme (CF3−O−(CF2−CF2−O)3−CF3), have been measured experimentally to validate the force field and increase our understanding of the physical properties of PFPEs. Force field parameters build upon those for related molecules (e.g., ethers and perfluoroalkanes) in the OPLS-AA force field, with new parameters introduced for interactions specific to PFPEs. Molecular dynamics simulations using the new force field demonstrate excellent agreement with ab initio calculations at the RHF/6-31G* level for gas-phase torsional energies (<0.5 kcal mol−1 error) and molecular structures for several PFPEs, and also accurately reproduce experimentally determined densities (<0.02 g cm−3 error) and enthalpies of vaporization derived from experimental vapor pressures (<0.3 kcal mol−1). Additional comparisons between experiment and simulation show that polyethers demonstrate a significant decrease in enthalpy of vaporization upon fluorination unlike related molecules (e.g., alkanes and alcohols). Simulation suggests this phenomenon is a result of reduced cohesion in liquid PFPEs due to a reduction in localized associations between backbone oxygen atoms and neighboring molecules

Vapor pressure and liquid density of fluorinated alcohols:Experimental, simulation and GC-SAFT-VR predictions

The vapor pressure of four liquid 1H,1H-perfluoroalcohols (CF3(CF2)n(CH2)OH, n ¼ 1, 2, 3, 4), often called odd-fluorotelomer alcohols, was measured as a function of temperature between 278 K and 328 K. Liquid densities were also measured for a temperature range between 278 K and 353 K. Molar enthalpies of vaporization were calculated from the experimental data. The results are compared with data from the literature for other perfluoroalcohols as well as with the equivalent hydrogenated alcohols. The results were modeled and interpreted using molecular dynamics simulations and the GC-SAFT-VR equation of state

GC- and UHPLC-MS Profiles as a Tool to Valorize the Red Alga Asparagopsis armata

Asparagopsis armata Harvey is a red alga native from the southern hemisphere and then introduced in the Mediterranean Sea and the Atlantic Ocean, including the Azores Archipelago, where it is considered an invasive alga. Some studies show that the extracts exhibit antimicrobial and antifouling activities, and it is incorporated in some commercialized cosmetic products. (e.g., Ysaline®). However, knowledge of this species chemical composition is scarce. The GC-MS and UHPLC-MS profiles of both the nonpolar and polar extracts were established to contribute to this problem solution. According to the results, A. armata is rich in a great structural variety of halogenated lipophilic and aromatic compounds, some of them identified here for the first time. In the lipophilic extract, 25 compounds are identified, being the halogenated compounds and fatty acids, the two major compound families, corresponding to 54.8% and 35.7% of identified compounds (224 and 147 mg/100 g of dry algae, respectively). The 1,4-dibromobuten-1-ol and the palmitic acid are the two most abundant identified compounds (155 and 83.4 mg/100 g of dry algae, respectively). The polar extract demonstrated the richness of this species in brominated phenolics, from which the cinnamic acid derivatives are predominant. The results obtained herein open new perspectives for valuing the A. armata as a source of halogenated compounds and fatty acids, consequently improving its biotechnological and economic potential. Promoting this seaweed and the consequent increase in its demand will contribute to biodiversity conservation and ecosystem sustainability.This study was financed by ASPAZOR project (DRCT: ACORES-01-0145-FEDER-00060- ASPAZOR); Portuguese National Funds, through FCT-Fundação para a Ciência e a Tecnologia, and as applicable co-financed by the FEDER within the PT2020 Partnership Agreement by funding the LAQV-REQUIMTE (UIDB/50006/2020) and the cE3c centre (FCT Unit funding (Ref. UID/BIA/00329/2013, 20152018) and UID/BIA/00329/2019).info:eu-repo/semantics/publishedVersio

Handheld near-infrared spectroscopy: state-of-the-art instrumentation and applications in material identification, food authentication, and environmental investigations

This present review article considers the rapid development of miniaturized handheld near-infrared spectrometers over the last decade and provides an overview of current instrumental developments and exemplary applications in the fields of material and food control as well as environmentally relevant investigations. Care is taken, however, not to fall into the exaggerated and sometimes unrealistic narrative of some direct-to-consumer companies, which has raised unrealistic expectations with full-bodied promises but has harmed the very valuable technology of NIR spectroscopy, rather than promoting its further development. Special attention will also be paid to possible applications that will allow a clientele that is not necessarily scientifically trained to solve quality control and authentication problems with this technology in everyday life.info:eu-repo/semantics/publishedVersio

Probing the CP nature of the Higgs coupling in tt¯h events at the LHC

The determination of the CP nature of the Higgs coupling to top quarks is addressed in this paper, using t¯th events produced in √s=13  TeV proton-proton collisions at the LHC. Dileptonic final states are employed, with two oppositely charged leptons and four jets, corresponding to the decays t→bW+→bℓ+νℓ, ¯t→¯bW−→¯bℓ−¯νℓ, and h→b¯b. Pure scalar (h=H), pure pseudoscalar (h=A), and CP-violating Higgs boson signal events, generated with MadGraph5_aMC@NLO, are fully reconstructed through a kinematic fit. We furthermore generate samples that have both a CP-even and a CP-odd component in the t¯th coupling in order to probe the ratio of the two components. New angular distributions of the decay products, as well as CP angular asymmetries, are explored in order to separate the scalar from the pseudoscalar components of the Higgs boson and reduce the contribution from the dominant irreducible background, t¯tb¯b. Significant differences between the angular distributions and asymmetries are observed, even after the full kinematic fit reconstruction of the events, allowing to define the best observables for a global fit of the Higgs couplings parameters.info:eu-repo/semantics/publishedVersio

Photocatalytic ozonation of urban wastewater and surface water using immobilized TiO2 with LEDs: Micropollutants, antibiotic resistance genes and estrogenic activity

Photocatalytic ozonation was employed for the first time in continuous mode with TiO2-coated glass Raschig rings and light emitting diodes (LEDs) to treat urban wastewater as well as surface water collected from the supply area of a drinking water treatment plant (DWTP). Different levels of contamination and types of contaminants were considered in this work, including chemical priority substances (PSs) and contaminants of emerging concern (CECs), as well as potential human opportunistic antibiotic resistant bacteria and their genes (ARB&ARG). Photocatalytic ozonation was more effective than single ozonation (or even than TiO2 catalytic ozonation) in the degradation of typical reaction by-products (such as oxalic acid), and more effective than photocatalysis to remove the parent micropollutants determined in urban wastewater. In fact, only fluoxetine, clarithromycin, erythromycin and 17-alpha-ethinylestradiol (EE2) were detected after photocatalytic ozonation, by using solid-phase extraction (SPE) pre-concentration and LC-MS/MS analysis. In surface water, this treatment allowed the removal of all determined micropollutants to levels below the limit of detection (0.01-0.20 ng L(-1)). The efficiency of this process was then assessed based on the capacity to remove different groups of cultivable microorganisms and housekeeping (16S rRNA) and antibiotic resistance or related genes (intI1, blaTEM, qnrS, sul1). Photocatalytic ozonation was observed to efficiently remove microorganisms and ARGs. Although after storage total heterotrophic and ARB (to ciprofloxacin, gentamicin, meropenem), fungi, and the genes 16S rRNA and intI1, increased to values close to the pre-treatment levels, the ARGs (blaTEM, qnrS and sul1) were reduced to levels below/close to the quantification limit even after 3-days storage of treated surface water or wastewater. Yeast estrogen screen (YES), thiazolyl blue tetrazolium reduction (MTT) and lactate dehydrogenase (LDH) assays were also performed before and after photocatalytic ozonation to evaluate the potential estrogenic activity, the cellular metabolic activity and the cell viability. Compounds with estrogenic effects and significant differences concerning cell viability were not observed in any case. A slight cytotoxicity was only detected for Caco-2 and hCMEC/D3 cell lines after treatment of the urban wastewater, but not for L929 fibroblasts.info:eu-repo/semantics/acceptedVersio

The effect of the Messinian salinity crisis on the early diversification of the Tettigettalna cicadas

The current distribution patterns of many Mediterranean species are often a consequence of large and impactful past geoclimatic events, such as the Messinian Salinity Crisis (MSC) and the Quaternary glacial cycles. Cicadas are flying insects with poor dispersal ability, which have experienced intense local differentiation in the Mediterranean, where the genus Tettigettalna has surfaced as a biogeographic model. The genus includes 10 species with species-specific calling songs but identical morphology. All Tettigettalna species are restricted to Southern Iberia, with the exception of T. estrellae (northwest Iberia), the widespread T. argentata (mainly Iberia, France and Italy), and T. afroamissa (Morocco). With an expanded genetic dataset involving nuclear (EF1α) and mitochondrial (5′ and 3′ COI and ATP) loci, we reconstructed the phylogeny of the genus and estimated divergence dates for Tettigettalna species under a Bayesian framework. Phylogeny with the new mitochondrial dataset was in agreement with previous studies, whereas the nuclear EF1α supported T. josei and T. afroamissa as monophyletic clades but lacked resolution to resolve the remaining taxa. Some sister taxa share mitochondrial haplotypes, hinting for incomplete lineage sorting. Estimates of divergence time settled T. josei as the earliest diverging lineage, likely as a pre- or early-MSC event. As for the origin of T. afroamissa in Morocco, though time estimates could not entirely rule out post-MSC dispersal, the most likely scenario points to isolation of African Tettigettalna after the reopening of the strait of Gibraltar. The Pleistocene glaciations that followed likely impacted on the diversification of the remaining species of the genus in southern Iberia refugia.info:eu-repo/semantics/submittedVersio

Early development of Moniliophthora perniciosa basidiomata and developmentally regulated genes

<p>Abstract</p> <p>Background</p> <p>The hemibiotrophic fungus <it>Moniliophthora perniciosa </it>is the causal agent of Witches' broom, a disease of <it>Theobroma cacao</it>. The pathogen life cycle ends with the production of basidiocarps in dead tissues of the infected host. This structure generates millions of basidiospores that reinfect young tissues of the same or other plants. A deeper understanding of the mechanisms underlying the sexual phase of this fungus may help develop chemical, biological or genetic strategies to control the disease.</p> <p>Results</p> <p>Mycelium was morphologically analyzed prior to emergence of basidiomata by stereomicroscopy, light microscopy and scanning electron microscopy. The morphological changes in the mycelium before fructification show a pattern similar to other members of the order <it>Agaricales</it>. Changes and appearance of hyphae forming a surface layer by fusion were correlated with primordia emergence. The stages of hyphal nodules, aggregation, initial primordium and differentiated primordium were detected. The morphological analysis also allowed conclusions on morphogenetic aspects. To analyze the genes involved in basidiomata development, the expression of some selected EST genes from a non-normalized cDNA library, representative of the fruiting stage <it>of M. perniciosa</it>, was evaluated. A macroarray analysis was performed with 192 selected clones and hybridized with two distinct RNA pools extracted from mycelium in different phases of basidiomata formation. This analysis showed two groups of up and down-regulated genes in primordial phases of mycelia. Hydrophobin coding, glucose transporter, Rho-GEF, Rheb, extensin precursor and cytochrome p450 monooxygenase genes were grouped among the up-regulated. In the down-regulated group relevant genes clustered coding calmodulin, lanosterol 14 alpha demethylase and PIM1. In addition, 12 genes with more detailed expression profiles were analyzed by RT-qPCR. One aegerolysin gene had a peak of expression in mycelium with primordia and a second in basidiomata, confirming their distinctiveness. The number of transcripts of the gene for plerototolysin B increased in reddish-pink mycelium and indicated an activation of the initial basidiomata production even at this culturing stage. Expression of the glucose transporter gene increased in mycelium after the stress, coinciding with a decrease of adenylate cyclase gene transcription. This indicated that nutrient uptake can be an important signal to trigger fruiting in this fungus.</p> <p>Conclusion</p> <p>The identification of genes with increased expression in this phase of the life cycle of <it>M. perniciosa </it>opens up new possibilities of controlling fungus spread as well as of genetic studies of biological processes that lead to basidiomycete fruiting. This is the first comparative morphologic study of the early development both <it>in vivo </it>and <it>in vitro </it>of <it>M. perniciosa </it>basidiomata and the first description of genes expressed at this stage of the fungal life cycle.</p

Exploring Metabolic Signatures of Ex Vivo Tumor Tissue Cultures for Prediction of Chemosensitivity in Ovarian Cancer

Predicting patient response to treatment and the onset of chemoresistance are still major challenges in oncology. Chemoresistance is deeply influenced by the complex cellular interactions occurring within the tumor microenvironment (TME), including metabolic crosstalk. We have previously shown that ex vivo tumor tissue cultures derived from ovarian carcinoma (OvC) resections retain the TME components for at least four weeks of culture and implemented assays for assessment of drug response. Here, we explored ex vivo patient-derived tumor tissue cultures to uncover metabolic signatures of chemosensitivity and/or resistance. Tissue cultures derived from nine OvC cases were challenged with carboplatin and paclitaxel, the standard-of-care chemotherapeutics, and the metabolic footprints were characterized by LC-MS. Partial least-squares discriminant analysis (PLS-DA) revealed metabolic signatures that discriminated high-responder from low-responder tissue cultures to ex vivo drug exposure. As a proof-of-concept, a set of potential metabolic biomarkers of drug response was identified based on the receiver operating characteristics (ROC) curve, comprising amino acids, fatty acids, pyrimidine, glutathione, and TCA cycle pathways. Overall, this work establishes an analytical and computational platform to explore metabolic features of the TME associated with response to treatment, which can leverage the discovery of biomarkers of drug response and resistance in OvC.publishersversionpublishe