Silver-Catalyzed C-C Bond Formation between Methane and Ethyl Diazoacetate in Supercritical CO2

Even in the context of hydrocarbons’ general resistance to selective functionalization, methane’s volatility and strong bonds pose a particular challenge. We report here that silver complexes bearing perfluorinated indazolylborate ligands catalyze the reaction of methane (CH4) with ethyl diazoacetate (N2CHCO2Et) to yield ethyl propionate (CH3CH2CO2Et). The use of supercritical carbon dioxide (scCO2) as the solvent is key to the reaction’s success. Although the catalyst is only sparingly soluble in CH4/CO2 mixtures, optimized conditions presently result in a 19% yield of ethyl propionate (based on starting quantity of the diazoester) at 40°C over 14 hours.Ministerio de Ciencia e Innovación (grants CTQ2008-00042-BQU, CTQ2007-65251-BQU, and CTQ2007-30762-E), the European Research Area Chemistry Programme (2nd call “Chemical activation of carbon dioxide and methane” contract no. 1736154), the Consolider Ingenio 2010 (grants CSD2006-003 and CSD2007-00006), the Institut de Chimie of the CNRS, the Junta de Andalucía (P07-FQM-2870), and the Generalitat Velenciana (ACOMP/2010/155).We dedicate this work to Professor Ernesto Carmona. Support for this work was provided by the Ministerio de Ciencia e Innovacion (grants CTQ2008-00042-BQU, CTQ2007-65251-BQU, and CTQ2007-30762-E), the European Research Area Chemistry Programme (2nd call "Chemical activation of carbon dioxide and methane" contract no. 1736154), the Consolider Ingenio 2010 (grants CSD2006-003 and CSD2007-00006), the Institut de Chimie of the CNRS, the Junta de Andalucia (P07-FQM-2870), and the Generalitat Velenciana (ACOMP/2010/155). We thank the Servicio Central de Soporte a la Investigacion Experimental (Universidad de Valencia) for access to the instrumental facilities and J. de la Rosa and A. Sanchez de la Campa (Universidad de Huelva) for ICP-MS analyses

Catalytic activity of MWCNT-based inks synthetized by different methods

Abstract of the poster presented at "Current Trends in Electrochemistry", 41st Meeting of the Electrochemistry Group of the Spanish Royal Society of Chemistry and 1st French-Spanish Atelier/Workshop on Electrochemistry, Paris (July 6 - 9, 2021).Research on new catalyst materials for the oxygen reduction reaction (ORR) is the main goal for many research groups around the world, due to its application in fuel cells and metal/air batteries. ORR mainly occurs by two pathways, in alkaline media, the direct four-electron transfer pathway from O2 to OH- or in a two-steps mechanism, where hydrogen peroxide (HO2-) is formed in the first reaction. On fuel cells and metal air batteries applications, the catalyst must be optimized to get the oxygen reduced directly to water through the 4 electrons mechanism1. Due to high price of the precious metals, new materials are tested to be used as catalyst in ORR. Among them, researchers have focused their attention mainly on metal oxides, perovskites or carbonaceous materials. In this communication, we have studied four carbonaceous-based inks synthetized by ultrasonic or hydrothermal methods2, using a rotating ring-disk electrode (RRDE) (Figure 1.A). The production of HO2- (%HO2-), transferred electrons and others parameters will be analyzed and the results will be discussed in depth. Finally, the inks were used as catalysts in the cathode of a PVA-KOH-based zinc/air batteries to replace the most widely used catalyst to date, MnO2The authors thank the financial support from Fundación Séneca (Región de Murcia, Spain; Ref: 20985/PI/18 and 19882-GERM-15), Spanish Agencia Estatal de Investigación (PID2019-104272RB-C55/ AEI/10.13039/501100011033 and PID2019-104272RB-C51/AEI/10.13039/501100011033), and Gobierno de Aragón (DGA T03_20R).Peer reviewe

Soluciones Creativas de Intervención (LUGH)

En este texto se puede encontrar información sobre los antecedentes del proyecto LUGH ITESO Soluciones creativas de intervención, así como los objetivos del trabajo que incluyen la vinculación entre empresas socialmente responsables con escenarios, comunidades, organizaciones u otros esfuerzos de la sociedad por mejorar su entorno. De este modo la empresa obtiene un beneficio en términos de posicionamiento, a la vez que produce un beneficio social tangible. Durante el período primavera 2016, se desarrollaron estrategias y piezas de comunicación para las organizaciones Plenitud de vida, Concertando México, Juntos por los demás y Capeltic. En este informe se incluye también la descripción del método de trabajo que el proyecto propone para la realización de estrategias de comunicación e intervención social

miR-16 and miR-125b are involved in barrier function dysregulation through the modulation of claudin-2 and cingulin expression in the jejunum in IBS with diarrhoea

Micro-RNAs (miRNAs) play a crucial role in controlling intestinal epithelial barrier function partly by modulating the expression of tight junction (TJ) proteins. We have previously shown differential messenger RNA (mRNA) expression correlated with ultrastructural abnormalities of the epithelial barrier in patients with diarrhoea-predominant IBS (IBS-D). However, the participation of miRNAs in these differential mRNA-associated findings remains to be established. Our aims were (1) to identify miRNAs differentially expressed in the small bowel mucosa of patients with IBS-D and (2) to explore putative target genes specifically involved in epithelial barrier function that are controlled by specific dysregulated IBS-D miRNAs. Healthy controls and patients meeting Rome III IBS-D criteria were studied. Intestinal tissue samples were analysed to identify potential candidates by: (a) miRNA-mRNA profiling; (b) miRNA-mRNA pairing analysis to assess the co-expression profile of miRNA-mRNA pairs; (c) pathway analysis and upstream regulator identification; (d) miRNA and target mRNA validation. Candidate miRNA-mRNA pairs were functionally assessed in intestinal epithelial cells. IBS-D samples showed distinct miRNA and mRNA profiles compared with healthy controls. TJ signalling was associated with the IBS-D transcriptional profile. Further validation of selected genes showed consistent upregulation in 75% of genes involved in epithelial barrier function. Bioinformatic analysis of putative miRNA binding sites identified hsa-miR-125b-5p and hsa-miR-16 as regulating expression of the TJ genes CGN (cingulin) and CLDN2 (claudin-2), respectively. Consistently, protein expression of CGN and CLDN2 was upregulated in IBS-D, while the respective targeting miRNAs were downregulated. In addition, bowel dysfunction, perceived stress and depression and number of mast cells correlated with the expression of hsa-miR-125b-5p and hsa-miR-16 and their respective target proteins. Modulation of the intestinal epithelial barrier function in IBS-D involves both transcriptional and post-transcriptional mechanisms. These molecular mechanisms include miRNAs as master regulators in controlling the expression of TJ proteins and are associated with major clinical symptoms

Acute Stress Regulates Sex-Related Molecular Responses in the Human Jejunal Mucosa: Implications for Irritable Bowel Syndrome

Estrés agudo; Barrera intestinal; SexoEstrès agut; Barrera intestinal; SexeCute stress; Intestinal barrier; SexIrritable bowel syndrome (IBS) is a prevalent gastrointestinal disorder linked to intestinal barrier dysfunction and life stress. We have previously reported that female sex per se determines an increased susceptibility to intestinal barrier dysfunction after cold pain stress (CPS). We aimed to identify sex-related molecular differences in response to CPS in healthy subjects to understand the origin of sex bias predominance in IBS. In 13 healthy males and 21 females, two consecutive jejunal biopsies were obtained using Watson’s capsule, at baseline, and ninety minutes after CPS. Total mucosal RNA and protein were isolated from jejunal biopsies. Expression of genes related to epithelial barrier (CLDN1, CLDN2, OCLN, ZO-1, and ZO-3), mast cell (MC) activation (TPSAB1, SERPINA1), and the glucocorticoid receptor (NR3C1) were analyzed using RT-qPCR. NR3C1, ZO-1 and OCLN protein expression were evaluated through immunohistochemistry and western blot, and mucosal inflammation through MC, lymphocyte, and eosinophil numbering. Autonomic, hormonal, and psychological responses to CPS were monitored. We found an increase in jejunal MCs, a reduced CLDN1 and OCLN expression, and an increased CLDN2 and SERPINA1 expression 90 min after CPS. We also found a significant decrease in ZO-1, OCLN, and NR3C1 gene expression, and a decrease in OCLN protein expression only in females, when compared to males. CPS induced a significant increase in blood pressure, plasma cortisol and ACTH, and subjective stress perception in all participants. Specific and independent sex-related molecular responses in epithelial barrier regulation are unraveled by acute stress in the jejunum of healthy subjects and may partially explain female predominance in IBS.Supported in part by Fondo Europeo de Desarrollo Regional (FEDER), Fondo de Investigación Sanitaria and Centro de Investigación Biomédica en Red de Enfermedades Hepáticas y Digestivas (CIBEREHD), Instituto de Salud Carlos III, Subdirección General de Investigación Sanitaria, Ministerio de Economiá y Competitividad: CM08/00229 (BL); CM10/00155 (MP); EII2011-0035, CD15/00010, and MV17-00043 (BKRJ.); FI12/00254 (ESR.), PI17/0190 (JS), PI12/00314 and PI15/00301 (CAC), CIBEREHD CB06/04/0021 (JS, CAC.); Vall d’Hebron Institut de Recerca, Programa de becas predoctorales Amics de Vall d’Hebron: PRED-VHIR-2014-018 (MF), PRED-VHIR-2016-53 34 (CPC.)

G-arylated hydrogen-bonded cyclic tetramer assemblies with remarkable thermodynamic and kinetic stability

The preparation and self-assembly of novel G-C dinucleoside monomers that are equipped with electron-poor aryl groups at the G-N2 amino group have been studied. Such monomers associate via Watson-Crick H-bonding into discrete unstrained tetrameric macrocycles that arise as a thermodynamically and kinetically stabilized product in a wide variety of experimental conditions, including very polar solvent environments and low concentrations. G-arylation produces an increased stability of the cyclic assembly, as a result of a subtle interplay between enthalpic and entropic effects involving the solvent coordination sphereFunding from the European Research Council (ERC-StG 279548) and MINECO (CTQ2011-23659) is gratefully acknowledge

Decreased TESK1-mediated cofilin 1 phosphorylation in the jejunum of IBS-D patients may explain increased female predisposition to epithelial dysfunction

Disturbed intestinal epithelial barrier and mucosal micro-inflammation characterize irritable bowel syndrome (IBS). Despite intensive research demonstrating ovarian hormones modulation of IBS severity, there is still limited knowledge on the mechanisms underlying female predominance in this disorder. Our aim was to identify molecular pathways involved in epithelial barrier dysfunction and female predominance in diarrhea-predominant IBS (IBS-D) patients. Total RNA and protein were obtained from jejunal mucosal biopsies from healthy controls and IBS-D patients meeting the Rome III criteria. IBS severity was recorded based on validated questionnaires. Gene and protein expression profiles were obtained and data integrated to explore biological and molecular functions. Results were validated by western blot. Tight junction signaling, mitochondrial dysfunction, regulation of actin-based motility by Rho, and cytoskeleton signaling were differentially expressed in IBSD. Decreased TESK1-dependent cofilin 1 phosphorylation (pCFL1) was confirmed in IBS-D, which negatively correlated with bowel movements only in female participants. In conclusion, deregulation of cytoskeleton dynamics through TESK1/CFL1 pathway underlies epithelial intestinal dysfunction in the small bowel mucosa of IBS-D, particularly in female patients. Further understanding of the mechanisms involving sex-mediated regulation of mucosal epithelial integrity may have significant preventive, diagnostic, and therapeutic implications for IBS

Toxicity of wine effluents and assessment of a depuration system for their control: assay with tadpoles of Rhinella arenarum (BUFONIDAE)

We evaluated the toxicity of the winery effluent and the efficiency of a symbiotic depuration system by means an experiment with Rhinella arenarum tadpoles. The studied effluent was taken from warehouses during the cleaning season. These effluents subsequently subjected to the purification treatment under evaluation. The effluent samples differentiated into two treatment levels: “raw” where the effluent was evaluated with field conditions and “treated” where the effluent was previously filtered with the symbiotic depuration system. The results of the bioassays compared with the physicochemical parameters determined in the effluent samples. The lethal response had a clear-cut correspondence with the effluent quality assessed utilizing physicochemical parameters. In all cases, dilution of the samples resulted in a significant reduction of their toxicity. It concluded that (a) winery effluents could be harmful to tadpoles of R. arenarum, (b) the symbiotic purification system used to treat wine effluents it would produce a significant reduction in the contaminant levels of the effluent. However, this reduction in contaminant levels does not provide sufficient safety for the release of the effluents into the environment.Fil: Navas Romero, Ana Laura. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto Argentino de Investigaciones de las Zonas Áridas. Provincia de Mendoza. Instituto Argentino de Investigaciones de las Zonas Áridas. Universidad Nacional de Cuyo. Instituto Argentino de Investigaciones de las Zonas Áridas; ArgentinaFil: Herrera Moratta, Mario Andres. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto Argentino de Investigaciones de las Zonas Áridas. Provincia de Mendoza. Instituto Argentino de Investigaciones de las Zonas Áridas. Universidad Nacional de Cuyo. Instituto Argentino de Investigaciones de las Zonas Áridas; ArgentinaFil: Rodríguez, María Rosa. Universidad Nacional de San Juan. Facultad de Ingeniería; ArgentinaFil: Quiroga, Lorena Beatriz. Universidad Nacional de San Juan. Facultad de Filosofía, Humanidades y Artes. Instituto de Ciencias Básicas; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Juan; ArgentinaFil: Echegaray, Marcelo Eduardo. Universidad Nacional de San Juan. Facultad de Ingeniería; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Juan; ArgentinaFil: Sanabria, Eduardo Alfredo. Universidad Nacional de San Juan. Facultad de Filosofía, Humanidades y Artes. Instituto de Ciencias Básicas; Argentina. Universidad Nacional de Cuyo. Facultad de Ciencias Exactas y Naturales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Juan; Argentin

Cervical determinants of anal HPV infection and high-grade anal lesions in women: a collaborative pooled analysis

Cervical cancer screening might contribute to the prevention of anal cancer in women. We aimed to investigate if routine cervical cancer screening results-namely high-risk human papillomavirus (HPV) infection and cytohistopathology-predict anal HPV16 infection, anal high-grade squamous intraepithelial lesions (HSIL) and, hence, anal cancer.International Agency for Research on Cance

ER-Bound Protein Tyrosine Phosphatase PTP1B Interacts with Src at the Plasma Membrane/Substrate Interface

PTP1B is an endoplasmic reticulum (ER) anchored enzyme whose access to substrates is partly dependent on the ER distribution and dynamics. One of these substrates, the protein tyrosine kinase Src, has been found in the cytosol, endosomes, and plasma membrane. Here we analyzed where PTP1B and Src physically interact in intact cells, by bimolecular fluorescence complementation (BiFC) in combination with temporal and high resolution microscopy. We also determined the structural basis of this interaction. We found that BiFC signal is displayed as puncta scattered throughout the ER network, a feature that was enhanced when the substrate trapping mutant PTP1B-D181A was used. Time-lapse and co-localization analyses revealed that BiFC puncta did not correspond to vesicular carriers; instead they localized at the tip of dynamic ER tubules. BiFC puncta were retained in ventral membrane preparations after cell unroofing and were also detected within the evanescent field of total internal reflection fluorescent microscopy (TIRFM) associated to the ventral membranes of whole cells. Furthermore, BiFC puncta often colocalized with dark spots seen by surface reflection interference contrast (SRIC). Removal of Src myristoylation and polybasic motifs abolished BiFC. In addition, PTP1B active site and negative regulatory tyrosine 529 on Src were primary determinants of BiFC occurrence, although the SH3 binding motif on PTP1B also played a role. Our results suggest that ER-bound PTP1B dynamically interacts with the negative regulatory site at the C-terminus of Src at random puncta in the plasma membrane/substrate interface, likely leading to Src activation and recruitment to adhesion complexes. We postulate that this functional ER/plasma membrane crosstalk could apply to a wide array of protein partners, opening an exciting field of research