Coordination Chemistry of potentially S,N,N py -Tridentate Thiosemicarbazones with the {Re(CO)3 } + fragment and formation of hemiaminal derivatives

Nine potentially S,N,Npy-tridentate thiosemicarbazones (HL) derived from pyridine-2-carbaldehyde or 1-(2-pyridyl)ethanone have been prepared and fully characterized. The X-ray crystal structures of six of them and two hydrochlorides were determined and analyzed. The reaction of the [ReX(CH3CN)2(CO)3]/[ReX(CO)5] (X = Cl and Br) precursors with these ligands yielded different kinds of compounds: the adducts [ReX(HL)(CO)3], in which the ligands were S,N-bidentate; the trinuclear species [Re3Cl2(L23)(HL23)(CO)9]; and the thiosemicarbazonate compounds [Re(L)(CO)3], where the ligand is S,N,Npy-tridentate. Besides, the reaction in methanol or ethanol of the thiosemicarbazones derived from aldehydes yielded S,N,Npy-tridentate hemiaminal cationic [Re(HLOR)(CO)3]X and neutral [Re(LOMe)(CO)3] complexes after the coordinated ligand underwent addition of the alcohol group to the imine bond. The reactivity of the complex [ReX(HL)(CO)3] in MeOH and NEt3 led to the formation of dinuclear [Re2(L)2(CO)6], where the thiosemicarbazonate is again S,N-bidentate. The influence that the substituents on the thiosemicarbazone ligands have on the stability of the complexes and the effect of the reaction medium on the resulting compounds have been analyzed.Agencia Estatal de Investigación | Ref. PID2019-110218RB-I00Universidade de Vigo/CISU

Inquiry in the high school physics laboratory: Which conditions would be the best to practice kayaking?

Recepción: 29 de julio de 2016 | Revisión: 6 de septiembre de 2016 | Aceptado: 17 octubre de 2016Correspondencia: Beatriz Crujeiras Pérez. Universidad de Santiago de CompostelaEmail: [email protected] cambios sociales producidos en las últimas décadas han llevado al requerimiento de una modificación en la metodología de enseñanza hacia una fundamentación en la autonomía del alumnado y la contextualización del aprendizaje. Por este motivo cobra especial relevancia el papel del laboratorio y, sobre todo, de enfoques como el aprendizaje de las ciencias basado en la indagación. Teniendo en cuenta que, en general, las investigaciones muestran que la enseñanza a través de la indagación produce resultados positivos para el aprendizaje del alumnado, el objetivo de este estudio es analizar los desempeños del alumnado durante la realización de una actividad de indagación guiada en el laboratorio. El estudio se enmarca en la investigación cualitativa y se centra en el análisis de las producciones del alumnado a través de una rúbrica. Entre los resultados recogidos destaca la existencia de ciertas operaciones de indagación que entrañan una mayor complicación para los y las estudiantes, así como la dificultad en la adaptación al nuevo enfoque. Sin embargo, se puede observar también que la implantación de este tipo de experiencias fomenta el interés y favorece el desarrollo de la competencia científica.The social changes produced in the last decades have ended in the requirement of a change in the teaching methods aimed at developing students’ autonomy in learning and contextualization practices. For this reason the role of the laboratory in Science learning becomes very relevant, in particular approaches like inquiry-based learning. Taking into account that, research in the literature shows that teaching through inquiry produces positive results in students’ learning, the goal of this study is to analyse the students’ performances during the performance of a guided inquiry task in the laboratory. The study draws on qualitative research and the focus is on the analysis of students’ productions by means of a rubric. The main results highlight the existence of certain inquiry operations that students find difficult as well as the adaptation to the new approach. However, it can be also observed that the implementation of this type of experiences promotes students’ interest in learning and enables the development of scientific competence.Universidad de Granada. Departamento de Psicología Social. Proyecto de Innovación Docente ReiDoCre

Coordination modes of hydrazone and acyl-hydrazone ligands containing a pyridine group with the {Re(CO)3}+ fragment

Financiado para publicación en acceso aberto: Universidade de Vigo/CISUGFour acyl-hydrazones derived from 5-hydroxypicolinohydrazide and 4-hydroxybenzaldehyde (HL11), 2-fluoro-4-hydroxybenzaldehyde (HL12), 2,4-dihydroxybenzaldehyde (HL13) or 2-pyridinecarboxaldehyde (HL14) and two hydrazones derived from 2-hydrazino pyridine and 4-dimethylaminobenzaldehyde (HL21) or 4-diethylamino-2-hydroxybenzaldehyde (HL22) were synthesized and their X-ray structures determined. Twelve rhenium(I) complexes of formula [ReX(HLn)(CO)3] (X = Cl, Br) were obtained by treating these ligands with [ReX(CH3CN)2(CO)3], and the structures of some representative compounds were determined by X-ray diffraction. The coordination geometry around rhenium(I) can be described as octahedral, with three carbon atoms in a fac configuration, the halogen atom and two nitrogen atoms from the hydrazone chain and the pyridine group, respectively. The carbonyl group of the acyl-hydrazone ligands does not participate in coordination in any of complexes HL11–HL14. The coordination mode of the ligands in all complexes could be established by comparing the IR and 1H NMR spectra. Formation of the hydrazonate complexes only proved possible with the derivatives of HL22. A study of the corresponding single crystal showed the presence of the dimer [Re2(L22)2(CO)6], in which the phenolate group of the ligand of the dimer partner coordinates to rhenium after deprotonation. This same group is used to bind to the rhenium atom of the dimer partner at the position released by the halide.Agencia Estatal de Investigación | Ref. PID2019-110218RB-I0

Dissipation of three fungicides and their effects on anthocyanins and color of monastrell red wines

The effect of fungicides on fermentation is of paramount importance to control the quality and safety of wines. In this work, the quality (enological parameters, color, phenolic content, antioxidant activity, and fungicide residues) of wines from Monastrell grapes fortified with iprovalicarb, mepanipyrim, and tetraconazole fungicides was evaluated. Along the winemaking process, initial residues of mepanipyrim and tetraconazole were removed in more than 90% while the dissipation of iprovalicarb was around 73%. Significant statistical differences were found in the presence of iprovalicarb and mepanipyrim residues, especially at the highest concentration assayed. For both fungicides, increases in the volatile acidity (between 4 and 8.6 times), the lactic acid content (between 8.6 and 20.5 times), the percentage of polymeric anthocyanins (between 1.3 and 1.7 times), and also a slight increase of the total phenolic index and the total anthocyanin content determined by spectrophotometry were observed. On the contrary, the total monomeric anthocyanins content decreased about 16.3% and 28.6% in the presence of iprovalicarb and mepanipyrim, respectively. These results could be related to a higher development of acetic acid or lactic bacteria in the presence of these fungicides. The color of the final wines was also different in comparison with the control, with a higher yellow component, color intensity, tonality, and hue angle because of pH changes in the medium. Tetraconazole fermentations had a more similar trend to the control wine, probably due to the lower concentration of this fungicide in the grape must at the initial time. No effects on the antioxidant activity was observed for any of the target fungicides. A multivariate statistical analysis was done to view the interrelationships between different variables (color and anthocyanins profile). The obtained model allowed the wines to be separated according to the fungicide treatment applied.Interreg | Ref. 0377_IBERPHENOL_6_EMinisterio de Economía y Competitividad | Ref. AGL2015-66491-C2-1-

Effect of two anti-fungal treatments (metrafenone and boscalid plus kresoxim-methyl) applied to vines on the color and phenol profile of different red wines

The effect of two anti-fungal treatments (metrafenone and boscalid + kresoxim-methyl) on the color and phenolic profile of Tempranillo and Graciano red wines has been studied. To evaluate possible modifications in color and phenolic composition of wines, control and wines elaborated with treated grapes under good agricultural practices were analyzed. Color was assessed by Glories and CIELab parameters. Color changes were observed for treated wines with boscalid + kresoxim-methyl, leading to the production of wines with less color vividness. Phenolic profile was characterized by HPLC analysis. Boscalid + kresoxim-methyl treatment promoted the greatest decrease on the phenolic content in wines.Ministerio de Ciencia e Innovación | Ref. AGL2011-30378-C03-0

Evaluation of pleural effusion sCD26 and DPP-IV as diagnostic biomarkers in lung disease

In this study, we measured ADA and DPP-IV enzymatic activity and sCD26 concentration in 150 pleural effusion (PE) samples and tested for correlations between these and other cellular and biochemical measures. We found that DPP-IV in particular might improve the specificity (but not the sensitivity) of the ADA test for diagnosis of pulmonary tuberculosis, since half of the false ADA positive results in non-tuberculous PE were also DPP-IV positive. A percentage of patients with malignant PE were sCD26 or DPP-IV positive; however, some patients with benign PE also tested positive. As a pattern associated with DPP-IV (but not the CD26 protein) was observed in PE, we searched for a finding that might increase the value of these biomarkers for diagnosis of malignancy. The observed pattern was related to the presence of leukocytes, as indicated by correlations with the cell count, and to a band of 180 kDa, detected by immunoblottingThis research was partially supported by grants PS09-00405 and Research Intensification activity from the Fondo de Investigación Sanitaria (FIS) of the Instituto de Salud Carlos III (Spain) and funding from Xunta de Galicia and FEDER (CN 2011/024). We are grateful to the patients who participated and made the study possibleS

Contribution of critical doses of iprovalicarb, mepanipyrim and tetraconazole to the generation of volatile compounds from Monastrell-based wines

Financiado para publicación en acceso aberto: Universidade de Vigo/CISUGThe individual effects of iprovalicarb, mepanipyrim, and tetraconazole on the volatile composition and aromatic profile of Monastrell-based wines were evaluated. To date, no studies about the effect of these fungicides on Monastrell-based wines are available, and the effect on other grape varieties is also unknown. Fungicides were added separately in the cellar to the grape must at two concentration levels (4 and 10 mg/kg for iprovalicarb and mepanipyrim and 1 and 2.5 mg/kg for tetraconazole). The aromatic composition of the final wines was analysed by gas chromatography using flame ionisation and ion trap mass selective detectors. In the presence of fungicides, the most significant variations were observed for isoamyl acetate and 2-phenylethyl acetate (increasing between 20 and 43% compared with the control wine) and ethyl caprate and caprylate (increasing between 12 and 68%). Consequently, treated wines showed a higher global odourant intensity, with increased fresh fruit notes.Ministerio de Economía y Competitividad | Ref. AGL2015-66491-C2-1-RAgencia Estatal de Investigación | Ref. PID2019-105061RB-C2

Proteomic approach to improve the diagnosis of malignant pleural effusions

Comunicaciones a congreso

Mepanipyrim residues on pasteurized red must influence the volatile derived compounds from Saccharomyces cerevisiae metabolism

The impact of mepanipyrim (Mep) and its corresponding commercial formulation (Mep Form) on Saccharomyces cerevisiae metabolites was assessed, separately, by using laboratory-scale wine fermentation assays on pasteurized red must. The presence of Mep did not alter the fermentation course. With regard to volatiles formed at the intracellular level by fermenting yeast cells, Mep residues affected mainly the acetate and ethyl ester biochemical pathways. In particular, the target acetates showed a notorious increment, >90%, in presence of commercial Mep Form at the higher dose assayed. The addition of Mep and Mep Form, at both tested levels, highly increased ethyl caprylate (between 42 and 63%) and ethyl caprate (between 36 and 60%) contents as the same as their respective fatty acid precursors. No important effects were observed on colour and non-volatile pyranoanthocyanins, probably due to the low anthocyanin content characteristic of pasteurized musts.Xunta de Galicia | Ref. EM2013/004POCTEP | Ref. 0377_IBERPHENOL_6_EMinisterio de Economía y Competitividad | Ref. AGL2015-66491-C2-1-

Relationship Between Quorum Sensing and Secretion Systems

Quorum sensing (QS) is a communication mechanism between bacteria that allows specific processes to be controlled, such as biofilm formation, virulence factor expression, production of secondary metabolites and stress adaptation mechanisms such as bacterial competition systems including secretion systems (SS). These SS have an important role in bacterial communication. SS are ubiquitous; they are present in both Gram-negative and Gram-positive bacteria and in Mycobacterium sp. To date, 8 types of SS have been described (T1SS, T2SS, T3SS, T4SS, T5SS, T6SS, T7SS, and T9SS). They have global functions such as the transport of proteases, lipases, adhesins, heme-binding proteins, and amidases, and specific functions such as the synthesis of proteins in host cells, adaptation to the environment, the secretion of effectors to establish an infectious niche, transfer, absorption and release of DNA, translocation of effector proteins or DNA and autotransporter secretion. All of these functions can contribute to virulence and pathogenesis. In this review, we describe the known types of SS and discuss the ones that have been shown to be regulated by QS. Due to the large amount of information about this topic in some pathogens, we focus mainly on Pseudomonas aeruginosa and Vibrio spp