Effect of metal loading on the CO2 methanation: A comparison between alumina supported Ni and Ru catalysts

The hydrogenation of CO2 into CH4 from H2 produced by renewable energy is considered an interesting alternative in order to promote the development of such green energies. In the present work, the effect of Ni and Ru loadings on the catalytic performance of alumina-supported catalysts is studied for CO2 methanation reaction. All catalysts were prepared by wetness incipient impregnation, characterized by several techniques (N2-physisorption, CO2-TPD, XRD, H2-chemisorption, XPS and H2-TPR) and evaluated for CO2 methanation in a fixed bed reactor at GHSV=10,000 h−1 and W/FCO2 0 = 4.7 (g cat.) h mol−1. Characterization results showed that addition of increasing loadings of Ni and Ru lead to the formation of both CO2 adsorption and H2 dissociation active sites, which are necessary to carry out CO2 hydrogenation into methane. Easily reducible ruthenium was dispersed on γ-Al2O3 in form of large agglomerates, whereas Ni was better dispersed presenting a great interaction with the support. 12% Ni and 4% Ru resulted to be the optimal contents providing metal surfaces of 5.1 and 0.6m2 g−1, T50 values of 340 and 310 °C and activity being quite stable for 24 h-on-stream. In terms of turnover frequency (TOF), 4%Ru/Al2O3 catalyst was quite more efficient than 12%Ni/Al2O3, probably due to a greater ability of ruthenium to dissociate hydrogen. The apparent activation energies for alumina supported Ni and Ru were 129 and 84 kJ mol−1, respectively.The support from the Economy and Competitiveness Spanish Ministry (CTQ2015-67597-C2-1-R and CTQ2015-67597-C2-2-R MINECO-FEDER), the Basque Government (IT657-13 and IT1297-19) and the SGIker (Analytical Services) at the University of the Basque Country are acknowledged. One of the authors (AQ) also acknowledges University of the Basque Country by his PhD grant (PIF-15/351)

Ni/LnOx catalysts (Ln = La, Ce or Pr) for CO2 methanation

The effect of the LnOx support has been studied for Ni‐based CO2 methanation catalysts. 10 wt. % nickel catalysts with LaOx, CeO2 and PrOx supports have been prepared, characterized by N2 adsorption, XRD, XRF, TG‐MS (N2‐TPD and H2‐TPR) and XPS, and have been tested for CO2 methanation. The catalytic activity follows the trend Ni/CeO2 > Ni/PrOx >> Ni/LaOx, all catalysts being very selective towards CH4 formation. The activity depends both on the nature of the catalytic active sites and on the stability of the surface CO2 and H2O species. Ni/CeO2 is the most active catalyst because (i) the Ni2+‐ceria interaction leads to the formation of the highest population of active sites for CO2 dissociation, (ii) the reduced Ni0 sites where H2 dissociation takes place are the most electronegative and active, and (iii) the stability of surface CO2 and H2O species is lowest. Ni/LaOx achieves lower activity because of the strong chemisorption of H2O and CO2, which poison the catalyst surface, and because this support is not able to promote the formation of highly active sites for CO2 and H2 dissociation. The behavior of Ni/PrOx is intermediate, being slightly lower to that of Ni/CeO2 because the formation of active sites is not so efficient and because the stability of chemisorbed CO2 is slightly higher.The authors thank the financial support of Basque Government (Consolidated Group IT657-13), Spanish Ministry of Economy and Competitiveness (Projects CTQ2015-67597-C2-1-R and CTQ2015-67597-C2-2-R), and the EU (FEDER funding). ADQ thanks the Spanish Ministry of Education, Culture and Sports (grant FPU14/01178) and AQ the University of the Basque Country (grant PIF15/351)

p-SMAD2/3 and DICER promote pre-miR-21 processing during pressure overload-associated myocardial remodeling

AbstractTransforming growth factor-β (TGF-β) induces miR-21 expression which contributes to fibrotic events in the left ventricle (LV) under pressure overload. SMAD effectors of TGF-β signaling interact with DROSHA to promote primary miR-21 processing into precursor miR-21 (pre-miR-21). We hypothesize that p-SMAD-2 and -3 also interact with DICER1 to regulate the processing of pre-miR-21 to mature miR-21 in cardiac fibroblasts under experimental and clinical pressure overload. The subjects of the study were mice undergoing transverse aortic constriction (TAC) and patients with aortic stenosis (AS). In vitro, NIH-3T3 fibroblasts transfected with pre-miR-21 responded to TGF-β1 stimulation by overexpressing miR-21. Overexpression and silencing of SMAD2/3 resulted in higher and lower production of mature miR-21, respectively. DICER1 co-precipitated along with SMAD2/3 and both proteins were up-regulated in the LV from TAC-mice. Pre-miR-21 was isolated bound to the DICER1 maturation complex. Immunofluorescence analysis revealed co-localization of p-SMAD2/3 and DICER1 in NIH-3T3 and mouse cardiac fibroblasts. DICER1-p-SMAD2/3 protein–protein interaction was confirmed by in situ proximity ligation assay. Myocardial up-regulation of DICER1 constituted a response to pressure overload in TAC-mice. DICER mRNA levels correlated directly with those of TGF-β1, SMAD2 and SMAD3. In the LV from AS patients, DICER mRNA was up-regulated and its transcript levels correlated directly with TGF-β1, SMAD2, and SMAD3. Our results support that p-SMAD2/3 interacts with DICER1 to promote pre-miR-21 processing to mature miR-21. This new TGFβ-dependent regulatory mechanism is involved in miR-21 overexpression in cultured fibroblasts, and in the pressure overloaded LV of mice and human patients

Tear proteome analysis in ocular surface diseases using label-free LC-MS/MS and multiplexedmicroarray biomarker validation

We analyzed the tear film proteome of patients with dry eye (DE), meibomian gland dysfunction (MGD), and normal volunteers (CT). Tear samples were collected from 70 individuals. Of these, 37 samples were analyzed using spectral-counting-based LC-MS/MS label-free quantitation, and 33 samples were evaluated in the validation of candidate biomarkers employing customized antibody microarray assays. Comparative analysis of tear protein profiles revealed differences in the expression levels of 26 proteins, including protein S100A6, annexin A1, cystatin-S, thioredoxin, phospholipase A2, antileukoproteinase, and lactoperoxidase. Antibody microarray validation of CST4, S100A6, and MMP9 confirmed the accuracy of previously reported ELISA assays, with an area under ROC curve (AUC) of 87.5%. Clinical endpoint analysis showed a good correlation between biomarker concentrations and clinical parameters. In conclusion, different sets of proteins differentiate between the groups. Apolipoprotein D, S100A6, S100A8, and ceruloplasmin discriminate best between the DE and CT groups. The differences between antileukoproteinase, phospholipase A2, and lactoperoxidase levels allow the distinction between MGD and DE, and the changes in the levels of annexin A1, clusterin, and alpha-1-acid glycoprotein 1, between MGD and CT groups. The functional network analysis revealed the main biological processes that should be examined to identify new candidate biomarkers and therapeutic targets

Monitoring by in situ NAP-XPS of active sites for CO2 methanation on a Ni/CeO2 catalyst

Ni/CeO2 catalysts are very active and selective for total hydrogenation of CO2 to methane, but the nature of the active sites is still unclear. The surface of a Ni/CeO2 catalyst has been monitored under CO2 methanation conditions by Near Ambient Pressure-XPS (NAP-XPS) using synchrotron radiation, and has been concluded that the species involved in the redox processes taking place during the CO2 methanation mechanism are the Ni2+-CeO2/Ni0 and Ce4+/Ce3+ pairs. In addition, a small fraction of nickel is present on the catalyst surface forming NiO and Ni2+-carbonates/hydroxyls (around 20% of the total surface nickel), but these species do not participate in the redox processes of the methanation mechanism. Under CO2 methanation conditions the H2 reduction rate of the Ni2+-CeO2/Ni0 and Ce4+/Ce3+ couples is much faster than their CO2 reoxidation rate (2 times faster, at least, at 300ºC), but a certain proportion of nickel always remains oxidized under reaction conditions. The high activity of Ni/CeO2 catalysts for CO2 methanation is tentatively attributed to the simultaneous presence of Ni2+-CeO2 and Ni0 active sites where CO2 and H2 are expected to be efficiently dissociated, respectively.Generalitat Valenciana, Spain (PROMETEO/2018/0765) Ministry for Science and Innovation MICINN, Spain (Projects PID2019-105960RB-C21 and PID2019-105960RB-C22) Junta de Andalucía, Spain (Project P18-RTJ-2974); European Union’s Horizon 2020 Research and Innovation Program (Marie Skłodowska-Curie grant agreement No 713567) Science Foundation Ireland Research Centre, Ireland (award 12/RC/2278_P2) ALBA synchrotron, Spain (Proposal number: ID 2020094556)

The long noncoding RNA Wisper controls cardiac fibrosis and remodeling

Long noncoding RNAs (lncRNAs) are emerging as powerful regulators of cardiac development and disease. However, our understanding of the importance of these molecules in cardiac fibrosis is limited. Using an integrated genomic screen, we identified Wisper (Wisp2 super-enhancer–associated RNA) as a cardiac fibroblast–enriched lncRNA that regulates cardiac fibrosis after injury. Wisper expression was correlated with cardiac fibrosis both in a murine model of myocardial infarction (MI) and in heart tissue from human patients suffering from aortic stenosis. Loss-of-function approaches in vitro using modified antisense oligonucleotides (ASOs) demonstrated that Wisper is a specific regulator of cardiac fibroblast proliferation, migration, and survival. Accordingly, ASO-mediated silencing of Wisper in vivo attenuated MI-induced fibrosis and cardiac dysfunction. Functionally, Wisper regulates cardiac fibroblast gene expression programs critical for cell identity, extracellular matrix deposition, proliferation, and survival. In addition, its association with TIA1-related protein allows it to control the expression of a profibrotic form of lysyl hydroxylase 2, implicated in collagen cross-linking and stabilization of the matrix. Together, our findings identify Wisper as a cardiac fibroblast–enriched super-enhancer–associated lncRNA that represents an attractive therapeutic target to reduce the pathological development of cardiac fibrosis in response to MI and prevent adverse remodeling in the damaged heart

Improving quality of care and clinical outcomes for rectal cancer through clinical audits in a multicentre cancer care organisation

Introduction: Colorectal cancer treatment requires a complex, multidisciplinary approach. Because of the potential variability, monitoring through clinical audits is advisable. This study assesses the effects of a quality improvement action plan in patients with locally advanced rectal cancer and treated with radiotherapy. Methods: Comparative, multicentre study in two cohorts of 120 patients each, selected randomly from patients diagnosed with rectal cancer who had initiated radiotherapy with a curative intent. Based on the results from a baseline clinical audit in 2013, a quality improvement action plan was designed and implemented; a second audit in 2017 evaluated its impact. Results: Standardised information was present on 77.5% of the magnetic resonance imaging (MRI) staging reports. Treatment strategies were similar in all three study centres. Of the patients whose treatment was interrupted, just 9.7% received a compensation dose. There was an increase in MRI re-staging from 32.5 to 61.5%, and a significant decrease in unreported circumferential resection margins following neoadjuvant therapy (ypCRM), from 34.5 to 5.6% (p < 0.001). Conclusions: The comparison between two clinical audits showed improvements in neoadjuvant radiotherapy in rectal cancer patients. Some indicators reveal areas in need of additional efforts, for example to reduce the overall treatment time

A urinary fragment of mucin-1 subunit α is a novel biomarker associated with renal dysfunction in the general population

Introduction: Sequencing peptides included in the urinary proteome identifies the parent proteins and may reveal mechanisms underlying the pathophysiology of chronic kidney disease. Methods: In 805 randomly recruited Flemish individuals (50.8% women; mean age, 51.1 years), we determined the estimated glomerular filtration rate (eGFR) from serum creatinine using the Chronic Kidney Disease Epidemiology Collaboration (CKD-EPI) equation. We categorized eGFR according to the National Kidney Foundation Kidney Disease Outcomes Quality Initiative guideline. We analyzed 74 sequenced urinary peptides with a detectable signal in more than 95% of participants. Follow-up measurements of eGFR were available in 597 participants. Results: In multivariable analyses, baseline eGFR decreased (P ≤ 0.022) with urinary fragments of mucin-1 (standardized association size expressed in ml/min/1.73 m2, −4.48), collagen III (−2.84), and fibrinogen (−1.70) and was bi-directionally associated (P ≤ 0.0006) with 2 urinary collagen I fragments (+2.28 and −3.20). The eGFR changes over 5 years (follow-up minus baseline) resulted in consistent estimates (P ≤ 0.025) for mucin-1 (−1.85), collagen (−1.37 to 1.43) and fibrinogen (−1.45) fragments. Relative risk of having or progressing to eGFR &lt;60 ml/min/1.73 m2 was associated with mucin-1. Partial least-squares analysis confirmed mucin-1 as the strongest urinary marker associated with decreased eGFR, with a score of 2.47 compared with 1.80 for a collagen I fragment as the next contender. Mucin-1 predicted eGFR decline to &lt;60 ml/min/1.73 m2 over and above microalbuminuria (P = 0.011) and retained borderline significance (P = 0.05) when baseline eGFR was accounted for. Discussion: In the general population, mucin-1 subunit α, an extracellular protein that is shed from renal tubular epithelium, is a novel biomarker associated with renal dysfunction

Nitrogen and Phosphorous Retention in Tropical Eutrophic Reservoirs with Water Level Fluctuations: A Case Study Using Mass Balances on a Long-Term Series

Nitrogen and phosphorous loading drives eutrophication of aquatic systems. Lakes and reservoirs are often effective N and P sinks, but the variability of their biogeochemical dynamics is still poorly documented, particularly in tropical systems. To contribute to the extending of information on tropical reservoirs and to increase the insight on the factors affecting N and P cycling in aquatic ecosystems, we here report on a long-term N and P mass balance (2003–2018) in Valle de Bravo, Mexico, which showed that this tropical eutrophic reservoir lake acts as a net sink of N (−41.7 g N m y) and P (−2.7 g P m y), mainly occurring through net sedimentation, equivalent to 181% and 68% of their respective loading (23.0 g N m y and 4.2 g P m y). The N mass balance also showed that the Valle de Bravo reservoir has a high net N atmospheric influx (31.6 g N m y), which was 1.3 times the external load and likely dominated by N fixation. P flux was driven mainly by external load, while in the case of N, net fixation also contributed. During a period of high water level fluctuations, the net N atmospheric flux decreased by 50% compared to high level years. Our results outlining water regulation can be used as a useful management tool of water bodies, by decreasing anoxic conditions and net atmospheric fluxes, either through decreasing nitrogen fixation and/or promoting denitrification and other microbial processes that alleviate the N load. These findings also sustain the usefulness of long-term mass balances to assess biogeochemical dynamics and its variability.This research was funded by UNAM, PAPIIT-IN207702 and CONACYT-SEMARNAT, C01-1125 projects to M.M-

Burden and challenges of heart failure in patients with chronic kidney disease. A call to action

Patients with the dual burden of chronic kidney disease (CKD) and chronic congestive heart failure (HF) experience unacceptably high rates of symptom load, hospitalization, and mortality. Currently, concerted efforts to identify, prevent and treat HF in CKD patients are lacking at the institutional level, with emphasis still being placed on individual specialty views on this topic. The authors of this review paper endorse the need for a dedicated cardiorenal interdisciplinary team that includes nephrologists and renal nurses and jointly manages appropriate clinical interventions across the inpatient and outpatient settings. There is a critical need for guidelines and best clinical practice models from major cardiology and nephrology professional societies, as well as for research funding in both specialties to focus on the needs of future therapies for HF in CKD patients. The implementation of crossspecialty educational programs across all levels in cardiology and nephrology will help train future specialists and nurses who have the ability to diagnose, treat, and prevent HF in CKD patients in a precise, clinically effective, and cost-favorable manner.Los pacientes con enfermedad renal crónica (ERC) que desarrollan insuficiencia cardíaca (IC) congestiva crónica presentan cifras inaceptablemente altas de síntomas, hospitalización y mortalidad. Actualmente, se echan en falta iniciativas institucionales dirigidas a identificar, prevenir y tratar la IC en los pacientes con ERC de manera multidisciplinar, prevaleciendo las actuaciones de las especialidades individuales. Los autores de este artículo de revisión respaldan la necesidad de crear equipos multidisciplinares cardiorrenales, en los que participen nefrólogos y enfermeras renales, que gestionen colaborativamente las intervenciones clínicas apropiadas en los entornos de pacientes con ERC e IC hospitalizados y ambulatorios. Es necesario y urgente que se elaboren guías y modelos de práctica clínica sobre la ERC con IC por parte de las sociedades profesionales de cardiología y nefrología, así como financiación para la investigación concertada entre ambas especialidades sobre la necesidad de futuros tratamientos para la IC en pacientes con ERC. La implementación de programas educativos cardiorrenales a todos los niveles en cardiología y nefrología ayudará a formar a los futuros especialistas y enfermeras para que tengan la capacidad de diagnosticar, tratar y prevenir la IC en pacientes con ERC de manera precisa, clínicamente efectiva y económicamente favorabl