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Recyclable supported Pd-NHC catalytic systems for the copper free Sonogashira cross-coupling in flow
A new family of well-defined NHC-Pd complexes immobilised onto silica, alumina and titania is reported. The catalysts display activity and recyclability in the Sonogashira cross-coupling reactions under batch and continuous flow conditions. Under batch conditions the new catalytic systems were recycled up to four times with yields over 80%. These catalysts have a broad substrate scope of different aryl bromides and alkynes. The titania-supported catalysts show good conversions under continuous flow conditions at least over 8 hours on stream using MeOH as solvent.The research leading to these results has received funding from the European Research Council under the European Union's Seventh Framework Programme (EC FP7) Grant Agreement n. [NMP2-SL-2012-280827]. The authors are grateful to TECSPR14-1-0045; TECNIOspring programme, the Agency for Business Competitiveness of the Government of Catalonia, ACCIÓ, the Generalitat de Catalunya (2014SGR670). and the Spanish Ministerio de Economía y Competitividad (CTQ2016-75016-R) for
financial support
Sediments: sink, archive, and source of contaminants
Se ha publicado una corrección de este artículo el 03 February 2023 ; DOI: 10.1007/s11356-023-25555-y
Publicado en: Environmental Science and Pollution Research, Vol. 30, nº 12, March 2023, pp. 35514Sediments are sources and sinks of contaminants and play an important role in mediating pollutants across environmental compartments of terrestrial and aquatic ecosystems. In surface waters (lakes, slowly flowing or dammed rivers, estuaries, oceans), organic and inorganic contaminants are either dissolved or sorbed to suspended matter and sediment particles according to their chemical properties. In the case of strong sorption, settling of suspended particles and sediment formation scavenge contaminants out of the water phase, resulting in the accumulation of contaminants in the beds of rivers and lakes.5 página
Recovering Old Grapevine Varieties
[EN] In this work we report new findings related to the recovery of old vines in The Comunitat Valenciana (Spain), where great diversity of grapevines varieties was present prior the phylloxera arrival. New accessions of old varieties previously recovered by our group and in risk of disappearance were located. Accessions with new SSR profiles were also found and, in some cases, could be ascribed to old grapevine ampelonyms; new synonymies were also detected. Chlorotypes were determined in the recovered germplasm. Several actions for the preservation of the recovered accessions have been initiated.This work was supported by the projects 'Recuperacion de variedades de vid', AGCOOP_D/2018/007' (co-funded by FEADER, MAPA and Conselleria d'Agricultura, Desenvolupament Rural, Emergencia Climatica i Transicio Ecologica (Generatitat Valenciana) and MINECO CGL2015-708432-R (co-funded by FEDER). We thank the IMIDRA and The Domain the Vassal Collection that provided two accessions each used as controls in our workGarcía, J.; Peiró Barber, RM.; Martinez-Gil, F.; Soler, JX.; Jimenez, C.; Yuste Del Carmen, A.; Xirivella, C.... (2020). Recovering Old Grapevine Varieties. VITIS. 59(3):101-103. https://doi.org/10.5073/vitis.2020.59.101-103S10110359
Magnetically boosted 1D photoactive microswarm for COVID-19 face mask disruption
The recent COVID-19 pandemic has resulted in the massive discard of pandemic-related plastic wastes, causing serious ecological harm and a high societal burden. Most single-use face masks are made of synthetic plastics, thus their careless disposal poses a direct threat to wildlife as well as potential ecotoxicological effects in the form of microplastics. Here, we introduce a 1D magnetic photoactive microswarm capable of actively navigating, adhering to, and accelerating the degradation of the polypropylene microfiber of COVID-19 face masks. 1D microrobots comprise an anisotropic magnetic core (Fe3O4) and photocatalytic shell (Bi2O3/Ag), which enable wireless magnetic maneuvering and visible-light photocatalysis. The actuation of a programmed rotating magnetic field triggers a fish schooling-like 1D microswarm that allows active interfacial interactions with the microfiber network. The follow-up light illumination accelerates the disruption of the polypropylene microfiber through the photo-oxidative process as corroborated by morphological, compositional, and structural analyses. The active magnetic photocatalyst microswarm suggests an intriguing microrobotic solution to treat various plastic wastes and other environmental pollutants.Web of Science141art. no. 93
Telemedicine platform for health assessment remotely by an integrated nanoarchitectonics FePS3/rGO and Ti3C2-based wearable device
Due to the emergence of various new infectious (viral/bacteria) diseases, the remote surveillance of infected persons has become most important, especially if hospitals need to isolate infected patients to prevent the spreading of pathogens to health care personnel. Therefore, we develop a remote health monitoring system by integrating a stretchable asymmetric supercapacitor (SASC) as a portable power source with sensors that can monitor the human physical health condition in real-time and remotely. An abnormal body temperature and breathing rate could indicate a person's sickness/infection status. Here we integrated FePS3@graphene-based strain sensor and SASC into an all-in-one textile system and wrapped it around the abdomen to continuously monitor the breathing cycle of the person. The real body temperature was recorded by integrating the temperature sensor with the SASC. The proposed system recorded physiological parameters in real-time and when monitored remotely could be employed as a screening tool for monitoring pathogen infection status.Web of Science61art. no. 7
Electrochemical Impedance Spectroscopy (bio)sensing through hydrogen evolution reaction induced by gold nanoparticles
A new gold nanoparticle (AuNP) based detection strategy using Electrochemical Impedance Spectroscopy (EIS) through hydrogen evolution reaction (HER) is proposed. This EIS-HER method is used as an alternative to the conventional EIS based on [Fe(CN)] or [Ru(NH)] indicators. The proposed method is based on the HER induced by AuNPs. EIS measurements for different amounts of AuNP are registered and the charge transfer resistance (R) was found to correlate and be useful for their quantification. Moreover the effect of AuNP size on electrical properties of AuNPs for HER using this sensitive technique has been investigated. Different EIS-HER signals generated in the presence of AuNPs of different sizes (2, 5, 10, 15, 20, and 50nm) are observed, being the corresponding phenomena extendible to other nanoparticles and related catalytic reactions. This EIS-HER sensing technology is applied to a magneto-immunosandwich assay for the detection of a model protein (IgG) achieving improvements of the analytical performance in terms of a wide linear range (2-500ngmL) with a good limit of detection (LOD) of 0.31ngmL and high sensitivity. Moreover, with this methodology a reduction of one order of magnitude in the LOD for IgG detection, compared with a chroamperometric technique normally used was achieved
The proinflammatory mediator CD40 ligand is increased in the metabolic syndrome and modulated by adiponectin
OBJECTIVES: We hypothesized that the CD40/CD40 ligand (CD40L) system is up-regulated in the metabolic syndrome (MS) and modulated by adiponectin (AN). The objectives were: 1) to compare plasma and monocyte CD40L in patients with MS and controls and its association with clinical and biochemical parameters, 2) to investigate platelets as a source of soluble CD40L (sCD40L), and 3) to analyze the effects of AN on CD40/CD40L.
METHODS: Plasma sCD40L and AN were measured in 246 controls and 128 patients with MS by ELISA. Monocyte CD40/CD40L expression and platelet CD40L content and release were compared in patients with MS and controls. Monocytes and endothelial cells were cultured with AN and CD40/CD40L expression determined by real-time RT-PCR and Western blotting.
RESULTS: Patients with MS had higher sCD40L and lower AN levels than controls (0.89 +/- 0.1 vs. 0.76 +/- 0.07 ng/ml and 10.10 +/- 0.65 vs. 12.99 +/- 0.80 microg /ml, P < 0.05). Monocyte CD40/CD40L expression was higher (P < 0.05) in patients than controls (CD40: 1.31 +/- 0.31 vs. 0.80 +/- 0.14 arbitrary units; CD40L: 1.24 +/- 0.85 vs. 0.43 +/- 0.14 pg/microg protein). No differences were observed on CD40L content between resting platelets from patients with MS and controls (7.7 +/- 3.5 vs. 7.2 +/- 2.2 pg/microg protein). Stimulated platelets from patients with the MS released more (P < 0.05) sCD40L than controls (582 +/- 141 vs. 334 +/- 60% change vs. nonstimulated platelets). AN reduced CD40L mRNA and protein expression in monocytes from MS patients and endothelial cells.
CONCLUSIONS: The enhanced sCD40L and cellular CD40L expression in the MS suggests that CD40L is of pathophysiological relevance in MS. Also, a new antiinflammatory effect of AN is described through the modulation of the CD40/CD40L system
Aldosterone induces cardiotrophin-1 expression in HL-1 adult cardiomyocytes
Aldosterone (ALDO) may induce cardiac hypertrophy by nonhemodynamic mechanisms that are not completely defined. Cardiotrophin-1 (CT-1) is a cytokine that exerts hypertrophic actions on isolated cardiomyocytes and promotes cardiac hypertrophy in vivo. We investigated whether ALDO induces CT-1 expression in HL-1 cardiomyocytes aiming at the possibility that the cytokine is involved in ALDO-induced cardiomyocyte hypertrophy. mRNA and protein expression were quantified by RT-PCR and Western blot. Cardiomyocyte area, as an index of hypertrophy, was assayed by image analysis in phalloidin-stained HL-1 cells. ALDO addition to adult HL-1 cardiomyocytes increased (P<0.01) CT-1 mRNA and protein expression in a concentration-dependent manner. This effect was abrogated by actinomycin D, the mineralocorticoid and glucocorticoid receptor antagonists spironolactone and RU486, respectively, and the p38 MAPK blocker SB203580. CT-1 signaling pathway blockade with specific antibodies against the cytokine and its two receptor subunits avoided (P<0.01) alpha-sarcomeric actin and c-fos protein overexpression as well as cell size increase induced by ALDO in HL-1 cells. In vivo, a single ALDO injection acutely increased (P<0.01) the myocardial expression of CT-1 in C57BJ6 wild-type mice but not CT-1-null mice. The bolus of the mineralocorticoid increased (P<0.01) ANP and c-fos mRNA expression in the myocardium of wild-type mice, whereas no changes were observed in CT-1-null mice. In summary, ALDO induces CT-1 expression in adult HL-1 cardiomyocytes via genomic and nongenomic mechanisms. CT-1 up-regulation could have relevance in the direct hypertrophic effects of ALDO in cardiomyocytes
Clinical, biochemical, and genetic characterization of acute hepatic porphyrias in a cohort of Argentine patients
Background: Acute Hepatic Porphyrias (AHPs) are characterized by an acute neuroabdominal syndrome including both neuropsychiatric symptoms and neurodegenerative changes. Two main hypotheses explain the pathogenesis of nervous system dysfunction: (a) the ROS generation by autooxidation of 5-aminolevulinic acid accumulated in liver and brain; (b) liver heme deficiency and in neural tissues that generate an oxidative status, a component of the neurodegenerative process. Methods: We review results obtained from Acute Intermittent Porphyria (AIP) and Variegate Porphyria (VP) families studied at clinical, biochemical, and molecular level at the CIPYP in Argentina. The relationship between the porphyric attack and oxidative stress was also evaluated in AHP patients and controls, to identify a marker of neurological dysfunction. Results: We studied 116 AIP families and 30 VP families, 609 and 132 individuals, respectively. Genotype/phenotype relation was studied. Oxidative stress parameters and plasma homocysteine levels were measured in 20 healthy volunteers, 22 AIP and 12 VP individuals. Conclusion: No significant difference in oxidative stress parameters and homocysteine levels between the analyzed groups were found.Fil: Martinez, María del Carmen. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Centro de Investigaciones sobre Porfirinas y Porfirias. Universidad de Buenos Aires. Centro de Investigaciones sobre Porfirinas y Porfirias; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Biológica; ArgentinaFil: Cerbino, Gabriela Nora. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Centro de Investigaciones sobre Porfirinas y Porfirias. Universidad de Buenos Aires. Centro de Investigaciones sobre Porfirinas y Porfirias; ArgentinaFil: Granata, Bárbara Xoana. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Centro de Investigaciones sobre Porfirinas y Porfirias. Universidad de Buenos Aires. Centro de Investigaciones sobre Porfirinas y Porfirias; ArgentinaFil: Batlle, Alcira Maria del C.. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Centro de Investigaciones sobre Porfirinas y Porfirias. Universidad de Buenos Aires. Centro de Investigaciones sobre Porfirinas y Porfirias; ArgentinaFil: Parera, Victoria Estela. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Centro de Investigaciones sobre Porfirinas y Porfirias. Universidad de Buenos Aires. Centro de Investigaciones sobre Porfirinas y Porfirias; ArgentinaFil: Rossetti, Maria Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Centro de Investigaciones sobre Porfirinas y Porfirias. Universidad de Buenos Aires. Centro de Investigaciones sobre Porfirinas y Porfirias; Argentin
Matrix metalloproteinase-10 is upregulated by thrombin in endothelial cells and increased in patients with enhanced thrombin generation
OBJECTIVE: Thrombin is a multifunctional serine protease that promotes vascular proinflammatory responses whose effect on endothelial MMP-10 expression has not previously been evaluated.
METHODS AND RESULTS: Thrombin induced endothelial MMP-10 mRNA and protein levels, through a protease-activated receptor-1 (PAR-1)-dependent mechanism, in a dose- and time-dependent manner. This effect was mimicked by a PAR-1 agonist peptide (TRAP-1) and antagonized by an anti-PAR-1 blocking antibody. MMP-10 induction was dependent on extracellular regulated kinase1/2 (ERK1/2) and c-jun N-terminal kinase (JNK) pathways. By serial deletion analysis, site-directed mutagenesis and electrophoretic mobility shift assay an AP-1 site in the proximal region of MMP-10 promoter was found to be critical for thrombin-induced MMP-10 transcriptional activity. Thrombin and TRAP-1 upregulated MMP-10 in murine endothelial cells in culture and in vivo in mouse aorta. This effect of thrombin was not observed in PAR-1-deficient mice. Interestingly, circulating MMP-10 levels (P<0.01) were augmented in patients with endothelial activation associated with high (disseminated intravascular coagulation) and moderate (previous acute myocardial infarction) systemic thrombin generation.
CONCLUSIONS: Thrombin induces MMP-10 through a PAR-1-dependent mechanism mediated by ERK1/2, JNK, and AP-1 activation. Endothelial MMP-10 upregulation could be regarded as a new proinflammatory effect of thrombin whose pathological consequences in thrombin-related disorders and plaque stability deserve further investigation
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