Metodologia de la pràctica instrumental en l'educació primària: un cas pràctic al CEIP Tombatossals

Treball Final de Grau en Mestre o Mestra d'Educació Primària. Codi: MP1040. Curs acadèmic 2015-2016Una correcta formació musical està completament relacionada amb l’execució d’una pràctica instrumental. Aquesta engloba una gran varietat de conceptes i coneixements musicals, i és necessària la seua presència a les escoles d’Educació Primària. L’adquisició teòrica de qualsevol concepte ha d’anar lligada a una aplicació pràctica per a interioritzar aquest amb major grau d’enteniment. La interpretació musical per mitjà d’instruments fa que l’alumnat siga protagonista del seu propi aprenentatge. A més a més, si es parteix dels interessos dels alumnes, la motivació i la iniciativa per aprendre està totalment garantida. Els aspectes lúdics i dinàmics han d’estar presents en tot moment en el desenvolupament de les sessions a una aula de música. A continuació, exposem una innovadora forma d’adoptar la música a les escoles. Una metodologia que utilitza la pràctica instrumental com a eix vertebrador en l’aprenentatge de l’alumnat. Per comprovar els possibles resultats d’aquest mètode de treball apliquem aquest a un cas real en una aula d’Educació Primària

Seasonal variations of essential oils from five accessions of Mentha longifolia (L.) L. with selected chemical profiles

[EN] Essential oil (EO) yield and composition of five accessions ofMentha longifolia(L.) L. (leaves) were determined throughout their vegetative cycle by GC-MS and GC-FID analysis. These accessions were selected based on TLC profiles of dichloromethane extracts from wild individuals. The profile rich in alpha-terpinyl acetate and 8-acetoxy carvotanacetone has not been previously reported. The maximum value of EO yield was obtained in advanced flowering stage. The major composition changes were noted at the beginning of the vegetative cycle, whereas more stability was found during the flowering stage. Thus, significant changes in the major compounds were found in some accessions: piperitone and piperitenone oxides, alpha-terpineol acetate and 8-acetoxy carvotanacetone, which showed a considerable increase (6.0% to 20.1%) during the vegetative growth, the same way that pulegone and piperitenone oxide in other accessions. As biological activities depend on EO composition, the knowledge of its seasonal changes should be emphasized.Llorens Molina, JA.; Vacas, S.; Castell-Zeising, V.; Verdeguer Sancho, MM. (2020). Seasonal variations of essential oils from five accessions of Mentha longifolia (L.) L. with selected chemical profiles. Journal of Essential Oil Research. 32(5):1-10. https://doi.org/10.1080/10412905.2020.1773328S110325Chapter 1Introduction. (2015). Handbook of Essential Oils, 18-21. doi:10.1201/b19393-5De Sousa Barros, A., de Morais, S. M., Ferreira, P. A. T., Vieira, Í. G. P., Craveiro, A. A., dos Santos Fontenelle, R. O., … de Sousa, H. A. (2015). Chemical composition and functional properties of essential oils from Mentha species. Industrial Crops and Products, 76, 557-564. doi:10.1016/j.indcrop.2015.07.004Gupta, A. K., Mishra, R., Singh, A. K., Srivastava, A., & Lal, R. K. (2017). Genetic variability and correlations of essential oil yield with agro-economic traits in Mentha species and identification of promising cultivars. Industrial Crops and Products, 95, 726-732. doi:10.1016/j.indcrop.2016.11.041Moshrefi Araghi, A., Nemati, H., Azizi, M., Moshtaghi, N., Shoor, M., & Hadian, J. (2019). Assessment of phytochemical and agro-morphological variability among different wild accessions of Mentha longifolia L. cultivated in field condition. Industrial Crops and Products, 140, 111698. doi:10.1016/j.indcrop.2019.111698Mathela, C. S., Padalia, R. C., Chanotiya, C. S., & Tiwari, A. (2005). Carvone richMentha longifolia(Linn.): Chemical Variation and Commercial Potential. Journal of Essential Oil Bearing Plants, 8(2), 130-133. doi:10.1080/0972060x.2005.10643432Schippmann, U., Leaman, D., & Cunningham, A. B. (s. f.). A Comparison of Cultivation and Wild Collection of Medicinal and Aromatic Plants Under Sustainability Aspects. Wageningen UR Frontis Series, 75-95. doi:10.1007/1-4020-5449-1_6Németh, E. (2005). CHANGES IN ESSENTIAL OIL QUANTITY AND QUALITY INFLUENCED BY ONTOGENETIC FACTORS. Acta Horticulturae, (675), 159-165. doi:10.17660/actahortic.2005.675.23Pothier, J., Galand, N., El Ouali, M., & Viel, C. (2001). Comparison of planar chromatographic methods (TLC, OPLC, AMD) applied to essential oils of wild thyme and seven chemotypes of thyme. Il Farmaco, 56(5-7), 505-511. doi:10.1016/s0014-827x(01)01085-0Franz, C. M. (2010). Essential oil research: past, present and future. Flavour and Fragrance Journal, 25(3), 112-113. doi:10.1002/ffj.1983Oil Composition of Other Mentha Species and Hybrids. (2006). Mint, 341-362. doi:10.1201/9780849307980-15Younis, Y. M. H., & Beshir, S. M. (2004). Carvone-Rich Essential Oils fromMentha longifolia(L.) Huds. ssp.schimperiBriq. andMentha spicataL. Grown in Sudan. Journal of Essential Oil Research, 16(6), 539-541. doi:10.1080/10412905.2004.9698792Koliopoulos, G., Pitarokili, D., Kioulos, E., Michaelakis, A., & Tzakou, O. (2010). Chemical composition and larvicidal evaluation of Mentha, Salvia, and Melissa essential oils against the West Nile virus mosquito Culex pipiens. Parasitology Research, 107(2), 327-335. doi:10.1007/s00436-010-1865-3Nazem, V., Sabzalian, M. R., Saeidi, G., & Rahimmalek, M. (2019). Essential oil yield and composition and secondary metabolites in self- and open-pollinated populations of mint (Mentha spp.). Industrial Crops and Products, 130, 332-340. doi:10.1016/j.indcrop.2018.12.018Maffei, M. (1988). A chemotype ofMentha longifolia (L.) hudson particularly rich in piperitenone oxide. Flavour and Fragrance Journal, 3(1), 23-26. doi:10.1002/ffj.2730030105Segev, D., Nitzan, N., Chaimovitsh, D., Eshel, A., & Dudai, N. (2012). Chemical and Morphological Diversity in Wild Populations of Mentha longifolia in Israel. Chemistry & Biodiversity, 9(3), 577-588. doi:10.1002/cbdv.201100108Hajlaoui, H., Snoussi, M., Ben Jannet, H., Mighri, Z., & Bakhrouf, A. (2008). Comparison of chemical composition and antimicrobial activities ofMentha longifolia L. ssp.longifolia essential oil from two Tunisian localities (Gabes and Sidi Bouzid). Annals of Microbiology, 58(3), 513-520. doi:10.1007/bf03175551Abdel-Hameed, E.-S. S., Salman, M. S., Fadl, M. A., Elkhateeb, A., & Hassan, M. M. (2018). Chemical Composition and Biological Activity ofMentha longifoliaL. Essential Oil Growing in Taif, KSA Extracted by Hydrodistillation, Solvent Free Microwave and Microwave Hydrodistillation. Journal of Essential Oil Bearing Plants, 21(1), 1-14. doi:10.1080/0972060x.2018.1454343Zouari-Bouassida, K., Trigui, M., Makni, S., Jlaiel, L., & Tounsi, S. (2018). Seasonal Variation in Essential Oils Composition and the Biological and Pharmaceutical Protective Effects of Mentha longifolia Leaves Grown in Tunisia. BioMed Research International, 2018, 1-12. doi:10.1155/2018/7856517Soilhi, Z., Rhimi, A., Heuskin, S., Fauconnier, M. L., & Mekki, M. (2019). Essential oil chemical diversity of Tunisian Mentha spp. collection. Industrial Crops and Products, 131, 330-340. doi:10.1016/j.indcrop.2019.01.041Asghari, B., Zengin, G., Bahadori, M. B., Abbas-Mohammadi, M., & Dinparast, L. (2018). Amylase, glucosidase, tyrosinase, and cholinesterases inhibitory, antioxidant effects, and GC-MS analysis of wild mint (Mentha longifolia var. calliantha) essential oil: A natural remedy. European Journal of Integrative Medicine, 22, 44-49. doi:10.1016/j.eujim.2018.08.004Ibrahim, S. R. M., Abdallah, H. M., Mohamed, G. A., Farag, M. A., Alshali, K. Z., Alsherif, E. A., & Ross, S. A. (2016). Volatile oil profile of some lamiaceous plants growing in Saudi Arabia and their biological activities. Zeitschrift für Naturforschung C, 72(1-2), 35-41. doi:10.1515/znc-2015-0234Hussain, A. I., Anwar, F., Nigam, P. S., Ashraf, M., & Gilani, A. H. (2010). Seasonal variation in content, chemical composition and antimicrobial and cytotoxic activities of essential oils from four Mentha species. Journal of the Science of Food and Agriculture, 90(11), 1827-1836. doi:10.1002/jsfa.4021Baser, K. H. C., Kürkçüoglu, M., Tarimcilar, G., & Kaynak, G. (1999). Essential Oils ofMenthaSpecies from Northern Turkey. Journal of Essential Oil Research, 11(5), 579-588. doi:10.1080/10412905.1999.9701218Kokkini, S., & Papageorgiou, V. (1988). Constituents of Essential Oils fromMentha longifoliaGrowing Wild in Greece. Planta Medica, 54(01), 59-60. doi:10.1055/s-2006-962338De Frutos, M., Sanz, J., & Martínez-Castro, I. (1988). Simultaneous distillation-extraction (SDE) method in the qualitative and quantitative GC analysis of cheese volatile components. Chromatographia, 25(10), 861-864. doi:10.1007/bf02311418Croteau, R. (1991). Metabolism of Monoterpenes in Mint (Mentha) Species. Planta Medica, 57(S 1), S10-S14. doi:10.1055/s-2006-96022

Exploring matrix effects in liquid chromatography–tandem mass spectrometry determination of pesticide residues in tropical fruits

Tropical fruits are being increasingly consumed around the world because of their appreciated characteristics, particularly their high nutritional value and distinctive taste, which are different from those of traditional fruits. Owing to their introduction into international markets it is necessary to have a reliable analytical methodology available for the sensitive determination of pesticide residues in order to monitor the compliance of maximum residue limits (MRLs). From an analytical point of view, tropical fruits have generally been far less studied than other fruits frequently consumed in the European Union or USA, which are among the most important markets. In this work, LC–MS/MS-based methodology using a triple quadrupole analyzer was developed for the multi-residue determination of selected pesticides and metabolites in tropical fruits, which were selected among the most popular in Colombia, one of the most important suppliers of tropical fruits around the world. After selection of a QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe)-based sample treatment, the study focused on the evaluation of matrix effects, in order to find a simple way for their correction. Twelve different food matrices were selected to perform this study: the seven Colombian tropical fruits of highest value for domestic and international markets (uchuva, tamarillo, granadilla, gulupa, maracuya, papaya, and pithaya), and five more matrices highly consumed in Colombia (lulo, carambolo, feijoa, mangostan, and guayaba). Twenty compounds, including pesticides widely applied in tropical fruits pest control and several metabolites considered in residue definition, were used as model compounds in this work. Correction factors were used on the basis of calibration graphs obtained with standards in solvent and in matrix, and their usefulness was supported by validation of the method in all the matrices tested at 0.01 and 0.1 mg/kg. The analysis of real-world samples revealed the presence of several target compounds that were identified by the acquisition of two MS/MS transitions, and by ion intensity ratio and retention time agreement.Generalitat Valenciana (Research Group of Excellence Prometeo 2009/ 054 and Prometeo II 2014/023; Collaborative Research on Environment and Food-Safety, ISIC/2012/016

In vitro bioanalytical assessment of toxicity of wetland samples from Spanish Mediterranean coastline

Background Fresh water bodies represent less than 1% of overall amount of water on earth and ensuring their quality and sustainability is pivotal. Although several campaigns have been performed to monitor the occurrence of micropollutants by means of chemical analysis, this might not cover the whole set of chemicals present in the sample nor the potential toxic effects of mixtures of natural and anthropogenic chemicals. In this sense, by selecting relevant toxicity endpoints when performing in vitro bioanalysis, effect-based methodologies can be of help to perform a comprehensive assessment of water quality and reveal biological activities relevant to adverse health effects. However, no prior bioanalytical study was performed in wetland water samples from the Spanish Mediterranean coastline. Methods Eleven samples from relevant water bodies from the Spanish Mediterranean coastline were collected to monitor water quality on 8 toxicity endpoints. Aryl hydrocarbon receptor (AhR), androgenicity (AR+ and AR-), estrogenicity (ER+ and ER-), oxidative stress response (Nrf2) and vitamin D receptor (VDR+ and VDR-) reporter gene assays were evaluated. Results AhR was the reporter gene assay showing a more frequent response over the set of samples (activated by 9 out of 11 samples), with TCDD-eq in the range 7.7-22.2 pM. For AR, ER and VDR assays sporadic activations were observed. Moreover, no activity was observed on the Nrf2 reporter gene assay. Wastewater and street runaway streams from Valencia could be responsible for enhanced activities in one of the water inputs in the Natural Park 'L'Albufera'. Conclusions Water quality of relevant wetlands from the Spanish Mediterranean coastline has been evaluated. The utilization of a panel of 5 different bioassays to cover for different toxicity endpoints has demonstrated to be a good tool to assess water quality

Prediction of Retention Time and Collision Cross Section (CCSH plus , CCSH-, and CCSNa plus ) of Emerging Contaminants Using Multiple Adaptive Regression Splines

Ultra-high performance liquid chromatography coupled to ion mobility separation and high-resolution mass spectrometry instruments have proven very valuable for screening of emerging contaminants in the aquatic environment. However, when applying suspect or nontarget approaches (i.e., when no reference standards are available), there is no information on retention time (RT) and collision cross-section (CCS) values to facilitate identification. In silico prediction tools of RT and CCS can therefore be of great utility to decrease the number of candidates to investigate. In this work, Multiple Adaptive Regression Splines (MARS) were evaluated for the prediction of both RT and CCS. MARS prediction models were developed and validated using a database of 477 protonated molecules, 169 deprotonated molecules, and 249 sodium adducts. Multivariate and univariate models were evaluated showing a better fit for univariate models to the experimental data. The RT model (R2 = 0.855) showed a deviation between predicted and experimental data of +/- 2.32 min (95% confidence intervals). The deviation observed for CCS data of protonated molecules using the CCSH model (R2 = 0.966) was +/- 4.05% with 95% confidence intervals. The CCSH model was also tested for the prediction of deprotonated molecules, resulting in deviations below +/- 5.86% for the 95% of the cases. Finally, a third model was developed for sodium adducts (CCSNa, R2 = 0.954) with deviation below +/- 5.25% for 95% of the cases. The developed models have been incorporated in an open-access and user-friendly online platform which represents a great advantage for third-party research laboratories for predicting both RT and CCS data

Variation in the pattern of synthetic cannabinoid use by a female patient during 2018

El consumo de cannabinoides sintéticos es un problema creciente. En España, el número de incautaciones e intoxicaciones relacionadas con estas nuevas sustancias psicoactivas (NPS) es menor que en el resto de Europa. No obstante, el análisis de mezclas de hierbas vendidas en smart-shops y páginas web refleja que estos productos sí están llegando a la población española. En este trabajo, se estudia el patrón de consumo de cannabinoides sintéticos en la ciudad de Valencia (España), a través del análisis de preparados de hierbas para fumar, cigarros y muestras de orina de potenciales consumidores recogidas en diferentes Unidades de Conductas Adictivas (UCAs) de la ciudad. Se analizaron diferentes productos disponibles en una smart-shop de la localidad, así como hierbas recogidas en las UCAs. Los análisis por espectrometría de masas revelaron la presencia de los cannabinoides sintéticos XLR-11 y UR-144. Se analizó también la orina de una paciente de la UCA, atendida por supuesto consumo de cannabis, que mostraba signos de consumo, aunque los análisis rutinarios daban resultados negativos. Se encontraron metabolitos de estos cannabinoides, previamente reportados en bibliografía. Tras el verano de 2018, se incautaron nuevas muestras de hierbas y cigarros, identificando el peligroso cannabinoide 5F-ADB. En las muestras de orina también se detectaron los principales metabolitos reportados para este cannabinoide sintético, y también se identificó este compuesto en una nueva hierba de la smart-shop. Es interesante resaltar que este cambio de consumo coincide con la prohibición en España del XLR-11 en el mes de julio de 2018, ilustrando cómo la legislación de estos compuestos afecta a su disponibilidad y, por tanto, a su patrón de consumo.The consumption of synthetic cannabinoids is a growing problem. In Spain, the number of seizures and poisonings related to these new psychoactive substances (NPS) is less than in the rest of Europe. However, the analysis of herbal mixtures sold in smart shops and web pages reflects that these products are indeed reaching the Spanish population. In this work, the consumption pattern of synthetic cannabinoids in the city of Valencia (Spain) is studied, through the analysis of herbal preparations for smoking, cigarettes and urine samples of potential consumers collected in different Addictive Behavior Units (ABUs) ) from the city. Different products available at a local smart-shop were analyzed, as well as herbs collected in the UCAs. Mass spectrometric analysis revealed the presence of the synthetic cannabinoids XLR-11 and UR-144. The urine of a patient from the ABU, treated for alleged cannabis use, who showed signs of use, was also analysed, although routine analysis gave negative results. Metabolites of these cannabinoids were found, previously reported in the literature. Following the summer of 2018, new herb and cigar samples were seized, identifying the dangerous cannabinoid 5F-ADB. The main metabolites reported for this synthetic cannabinoid were also detected in the urine samples, and this compound was also identified in a new herb from the smart shop. It is interesting to note that this change in consumption coincides with the ban on XLR-11 in Spain in July 2018, illustrating how the legislation on these compounds affects their availability and, therefore, their consumption pattern

Gas chromatography-tandem mass spectrometry with atmospheric pressure chemical ionization for fluorotelomer alcohols and perfluorinated sulfonamides determination

Ionization and in source-fragmentation behavior of four fluorotelomer alcohols (FTOH) (4:2 FTOH, 6:2FTOH, 8:2 FTOH and 10:2 FTOH) and four N-alkyl fluorooctane sulfonamides/-ethanols (N-MeFOSA, N-EtFOSA, N-MeFOSE and N-EtFOSE) by APCI has been studied and compared with the traditionally usedEI and CI. Protonated molecule was the base peak of the APCI spectrum in all cases giving the possibilityof selecting it as a precursor ion for MS/MS experiments. Following, CID fragmentation showed commonproduct ions for all FOSAs/FOSEs (C4F7and C3F5). Nevertheless, the different functionality gave charac-teristic pattern fragmentations. For instance, FTOHs mainly loss H2O + HF, FOSAs showed the losses ofSO2and HF while FOSEs showed the losses of H2O and SO2. Linearity, repeatability and LODs have beenstudied obtaining instrumental LODs between 1 and 5 fg. Finally, application to river water and influentand effluent waste water samples has been carried out in order to investigate the improvements in detec-tion capabilities of this new source in comparison with the traditionally used EI/CI sources. Matrix effectsin APCI have been evaluated in terms of signal enhancement/suppression when comparing standardsin solvent and matrix. No matrix effects were observed and concentrations found in samples were inthe range of 1-100 pg L−1far below the LODs achieved with methods previously reported. Unknownrelated perfluoroalkyl substances, as methyl-sulfone and methyl-sulfoxide analogues for FTOHs, werealso discovered and tentatively identified

Intra- and Intermolecular Dispersion Interactions in [n]Cycloparaphenylenes: Do They Influence Their Structural and Electronic Properties?

Cycloparaphenylenes (CPPs) are nanosized structures with unique isolated and bulk properties, and are synthetic targets for the template-driven bottom-up synthesis of carbon nanotubes. Thus, a systematic understanding of the supramolecular order at the nanoscale is of utmost relevance for molecular engineering. In this study, it is found that intramolecular noncovalent (dispersion) interactions must be taken into account for obtaining accurate estimates of the structural and optoelectronic properties of [n]CPP compounds, and their influence as the number of repeat units increases from n=4 to n=12 is also analyzed, both in the gas phase and in solution. The supramolecular self-assembly, for which both intra- and intermolecular noncovalent interactions are relevant, of [6]CPP is also investigated by calculating the binding energies of dimers taken along several crystal directions. These are also used to estimate the cohesive energy of the crystal, which is compared to the value obtained by means of dispersion-corrected DFT calculations using periodic boundary conditions. The reasonable agreement between both computational strategies points towards a first estimate of the [6]CPP cohesive energy of around 50 kcal mol−1.This work is supported by the “Ministerio de Economia y Competitividad” of Spain and the “European Regional Development Fund” through projects CTQ2011-27253, CTQ2014-55073P and FIS2012-35880

Untargeted metabolomics approach for unraveling robust biomarkers of nutritional status in fasted gilthead sea bream (Sparus aurata)

A metabolomic study has been performed to identify sensitive and robust biomarkers of malnutrition in farmed fish, using gilthead sea bream (Sparus aurata) as a model. The metabolomic fingerprinting of serum from fasted fish was assessed by means of ultra-high performance liquid chromatography coupled to quadrupole time-offlight mass spectrometry. More than 15,000 different m/z ions were detected and Partial Least Squares–Discriminant analysis allowed a clear differentiation between the two experimental groups (fed and 10-day fasted fish) with more than 90% of total variance explained by the two first components. The most significant metabolites (up to 45) were elucidated on the basis of their tandem mass spectra with a broad representation of amino acids, oligopeptides, urea cycle metabolites, L-carnitinerelated metabolites, glutathione-related metabolites, fatty acids, lysophosphatidic acids, phosphatidylcholines as well as biotin- and noradrenaline-related metabolites. This untargeted approach highlighted important adaptive responses in energy and oxidative metabolism, contributing to identify robust and nutritionally-regulated biomarkers of health and metabolic condition that will serve to assess the welfare status of farmed fish.This work was supported by the Spanish MINECO (MI2-Fish, AGL2013-48560) and Plà de promoció de la investigació de la Universitat Jaume I (P1•1B2015-59) and the Generalitat Valenciana as research group of excellence (PROMETEO II/2014/023, PROMETEO II/2014/085, Collaborative Research on Environment and Food-Safety, ISIC/2012/016)

Untargeted metabolomics approach using UHPLC-IMS-QTOF MS for surface body samples to identify low-volatility chemosignals related to maternal care in mice

The present study is focused on the determination of low-volatile chemosignals excreted or secreted by mouse pups in their early days of life involved in maternal care induction in mice adult females. Untargeted metabolomics was employed to differentiate between samples collected with swabs from facial and anogenital area from neonatal mouse pups receiving maternal care (first two weeks of life) and the elder mouse pups in the weaning period (4th week old). The sample extracts were analysed by ultra-high pressure liquid chromatography (UHPLC) coupled to ion mobility separation (IMS) in combination with high resolution mass spectrometry (HRMS). After data processing with Progenesis QI and multivariate statistical analysis, five markers present in the first two weeks of mouse pups life and putatively involved in materno-filial chemical communication were tentatively identified: arginine, urocanic acid, erythro-sphingosine (d17:1), sphingosine (d18:1) and sphinganine. The four-dimensional data and the tools associated to the additional structural descriptor obtained by IMS separation were of great help in the compound identification. The results demonstrated the great potential of UHPLC-IMS-HRMS based untargeted metabolomics to identity putative pheromones in mammals.Funding for open access charge: CRUE-Universitat Jaume