Gold clusters immobilized by post-synthesis methods on thiol-containing SBA-15 mesoporous materials for the aerobic oxidation of cyclohexene: influence of light and hydroperoxide

Gold nanospecies produced by a historically inspired two-liquid phase system were immobilized on plate-like mesoporous silica, SBA-15, functionalized with mercaptopropyl groups by a post-synthesis method, and the resulting materials were tested in the oxidation of cyclohexene with molecular oxygen at atmospheric pressure. The main purpose of this approach was to compare the physicochemical properties and catalytic performance of these materials with those of previously reported related materials functionalized by in situ methods during synthesis. In addition, catalytic tests under ambient lighting and darkness and also in the presence and absence of the initiator tert-butyl hydroperoxide (TBHP) were carried out. The samples were characterized by chemical analysis, N2 adsorption/desorption, TGA, SEM, HRTEM, UV-vis spectroscopy and XPS. Gold nanoclusters and isolated gold atoms but no AuNPs were found in the catalysts (0.31–2.69 wt.% of gold). The XPS shows that nearly 60% of the -SH groups (1.33 wt.% of S) were oxidized to sulphonic groups upon gold immobilization. The AuNCs and isolated gold atoms evolved in the the reaction medium to form AuNPs. The activity of the samples was lower than that of the catalysts supported on related S-bearing SBA-15 functionalized in situ, which was attributed to their different Au/S ratios, which in turn regulated the evolutionary process of the gold species during the reaction. The catalysts turned out to be inactive in darkness, which evidences that the cyclohexene oxidation carried out at ambient illumination is actually photocatalyzed by the AuNPs formed in situ during the reaction. The TBHP initiator is required to obtain the activity in order to counteract the inhibitors of cyclohexene auto-oxidation present in the commercial reagent. On the other hand, no major differences in the selectivity among the different catalysts and reactions were observed, with 2-cyclohexen-1-one and 2-cyclohexen-1-ol resulting from the allylic oxidation as main products (selectivity of (one + ol) ~80% at a conversion ≥ 35%; one/ol~2)

Enantiosensitive growth dynamics of chiral molecules on ferromagnetic substrates and the origin of the CISS effect

The recent demonstration of the existence of an intimate relationship between the chiral structure of some materials and the spin polarization of electrons transmitted through them, what has been called the chirality-induced spin selectivity (CISS) effect, is sparking interest in many related phenomena. One of the most notorious is the possibility of using magnetic materials to apply enantioselective interactions on chiral molecules and chemical reactions involving them. In this work, x-ray photoelectron spectroscopy has been used to characterize the adsorption and growth kinetics of enantiopure organic molecules on magnetic (Co) and non-magnetic (Cu) substrates. While on these latter, no significant enantiosensitive effects are found, on spin-polarized, in-plane magnetized Co surfaces, the two enantiomers have been found to deposit differently. The observed effects have been interpreted as the result of one of the enantiomers being adsorbed in a transient, weakly bound physisorbed-like state with higher mobility due to limited, spin-selective charge transfer between it and the substrate. The study of these phenomena can provide insight into the fundamental mechanisms responsible for the CISS effectThis work was funded by the Spanish Ministry of Science and Innovation through Grant Nos. TED2021-131042B-I00 and PID2021-123295NB-I0

In vitro efficacy of several disinfectants against Salmonella enterica serovar Enteritidis and Escherichia coli strains from poultry = Eficácia de vários desinfetantes in vitro contra cepas de Salmonella enterica serovar Enteritidis e Escherichia coli aviária

5 p.The efficacy of 28 individual or blended disinfectants against avian Salmonella enterica serovar Enteritidis and Escherichia coli strains was determined. An in vitro test in the presence and absence of serum as source of organic material was conducted. Povidone-iodine (releasing 1% available iodine), 1% potassium permanganate, 70% ethanol, 2% chlorhexidine digluconate and three commercial formulations based on quaternary ammonium compounds + formaldehyde or cresol derivates were the most effective against all strains tested and reduced bacterial counts by more than 106 times (6-log10) regardless of the presence of organic matter. These commercial compounds as well as ethanol and chlorhexidine among the individual substances tested might be helpful in the adoption of environmental control measures against these two enterobacteria in poultry industryS

Characterization of chronic HCV infection in Northwest Spain: impact of the treatment strategic plan of the Spanish National Health Service on HCV cure

[Abstract] The aim of the study was to characterize HCV infection in Northwest Spain and assess the impact of the Spanish Strategic Plan to cure HCV infection. Overall, 387 patients were included (60.9% HIV/HCV coinfected and 28.2% cirrhotic). Of these, 72.9% of patients that were recognized as priority for HCV treatment according to the Spanish Strategic Plan (≥F2, transplant or extrahepatic manifestations), initiated treatment during 2015. Globally, SVR12 was achieved in 96.5% of patients. The implementation of the Spanish Strategic Plan has been critical to advance in HCV cure, but 27.1% of priority patients still remain awaiting HCV treatment initiation.Instituto de Salud Carlos III; CPII14/00014Instituto de Salud Carlos III; PI10/02166Instituto de Salud Carlos III; PI13/02266Instituto de Salud Carlos III; CM15/00233Instituto de Salud Carlos III; FI14/0055

National survey: how do we approach the patient at risk of clinical deterioration outside the ICU in the spanish context?

Background: Anticipating and avoiding preventable intrahospital cardiac arrest and clinical deterioration are important priorities for international healthcare systems and institutions. One of the internationally followed strategies to improve this matter is the introduction of the Rapid Response Systems (RRS). Although there is vast evidence from the international community, the evidence reported in a Spanish context is scarce. Methods: A nationwide cross-sectional research consisting of a voluntary 31-question online survey was performed. The Spanish Society of Intensive, Critical and Coronary Care Medicine (SEMICYUC) supported the research. Results: We received 62 fully completed surveys distributed within 13 of the 17 regions and two autonomous cities of Spain. Thirty-two of the participants had an established Rapid Response Team (RRT). Common frequency on measuring vital signs was at least once per shift but other frequencies were contemplated (48.4%), usually based on professional criteria (69.4%), as only 12 (19.4%) centers used Early Warning Scores (EWS) or automated alarms on abnormal parameters. In the sample, doctors, nurses (55%), and other healthcare professionals (39%) could activate the RRT via telephone, but only 11.3% of the sample enacted this at early signs of deterioration. The responders on the RRT are the Intensive Care Unit (ICU), doctors, and nurses, who are available 24/7 most of the time. Concerning the education and training of general ward staff and RRT members, this varies from basic to advanced and specific-specialized level, simulating a growing educational methodology among participants. A great number of participants have emergency resuscitation equipment (drugs, airway adjuncts, and defibrillators) in their general wards. In terms of quality improvement, only half of the sample registered RRT activity indicators. In terms of the use of communication and teamwork techniques, the most used is clinical debriefing in 29 centers. Conclusions: In terms of the concept of RRS, we found in our context that we are in the early stages of the establishment process, as it is not yet a generalized concept in most of our hospitals. The centers that have it are in still in the process of maturing the system and adapting themselves to our context

Characterization of a Ferryl Flip in Electronically Tuned Nonheme Complexes. Consequences in Hydrogen Atom Transfer Reactivity

Two oxoiron(IV) isomers (R2a and R2b) of general formula [FeIV(O)(RPyNMe3)(CH3CN)]2+ are obtained by reaction of their iron(II) precursor with NBu4IO4. The two isomers differ in the position of the oxo ligand, cis and trans to the pyridine donor. The mechanism of isomerization between R2a and R2b has been determined by kinetic and computational analyses uncovering an unprecedented path for interconversion of geometrical oxoiron(IV) isomers. The activity of the two oxoiron(IV) isomers in hydrogen atom transfer (HAT) reactions shows that R2a reacts one order of magnitude faster than R2b, which is explained by a repulsive noncovalent interaction between the ligand and the substrate in R2b. Interestingly, the electronic properties of the R substituent in the ligand pyridine ring do not have a significant effect on reaction rates. Overall, the intrinsic structural aspects of each isomer define their relative HAT reactivity, overcoming changes in electronic properties of the ligand.10 página

Characterization of a Ferryl Flip in Electronically Tuned Nonheme Complexes. Consequences in Hydrogen Atom Transfer Reactivity

Two oxoiron(IV) isomers (R2a and R2b) of general formula [FeIV(O)(RPyNMe3)(CH3CN)]2+ are obtained by reaction of their iron(II) precursor with NBu4IO4. The two isomers differ in the position of the oxo ligand, cis and trans to the pyridine donor. The mechanism of isomerization between R2a and R2b has been determined by kinetic and computational analyses uncovering an unprecedented path for interconversion of geometrical oxoiron(IV) isomers. The activity of the two oxoiron(IV) isomers in hydrogen atom transfer (HAT) reactions shows that R2a reacts one order of magnitude faster than R2b, which is explained by a repulsive noncovalent interaction between the ligand and the substrate in R2b. Interestingly, the electronic properties of the R substituent in the ligand pyridine ring do not have a significant effect on reaction rates. Overall, the intrinsic structural aspects of each isomer define their relative HAT reactivity, overcoming changes in electronic properties of the ligand

Comprehensive Analysis of SWI/SNF Inactivation in Lung Adenocarcinoma Cell Models

Simple Summary: Mammalian SWI/SNF complexes regulate gene expression by reorganizing the way DNA is packaged into chromatin. SWI/SNF subunits are recurrently altered in tumors at multiple levels, including DNA mutations as well as alteration of the levels of RNA and protein. Cancer cell lines are often used to study SWI/SNF function, but their patterns of SWI/SNF alterations can be complex. Here, we present a comprehensive characterization of DNA mutations and RNA and protein expression of SWI/SNF members in 38 lung adenocarcinoma (LUAD) cell lines. We show that over 85% of our cell lines harbored at least one alteration in one SWI/SNF subunit. In addition, over 75% of our cell lines lacked expression of at least one SWI/SNF subunit at the protein level. Our catalog will help researchers choose an appropriate cell line model to study SWI/SNF function in LUAD. Abstract: Mammalian SWI/SNF (SWitch/Sucrose Non-Fermentable) complexes are ATP-dependent chromatin remodelers whose subunits have emerged among the most frequently mutated genes in cancer. Studying SWI/SNF function in cancer cell line models has unveiled vulnerabilities in SWI/SNF-mutant tumors that can lead to the discovery of new therapeutic drugs. However, choosing an appropriate cancer cell line model for SWI/SNF functional studies can be challenging because SWI/SNF subunits are frequently altered in cancer by various mechanisms, including genetic alterations and post-transcriptional mechanisms. In this work, we combined genomic, transcriptomic, and proteomic approaches to study the mutational status and the expression levels of the SWI/SNF subunits in a panel of 38 lung adenocarcinoma (LUAD) cell lines. We found that the SWI/SNF complex was mutated in more than 76% of our LUAD cell lines and there was a high variability in the expression of the di erent SWI/SNF subunits. These results underline the importance of the SWI/SNF complex as a tumor suppressor in LUAD and the di culties in defining altered and unaltered cell models for the SWI/SNF complex. These findings will assist researchers in choosing the most suitable cellular models for their studies of SWI/SNF to bring all of its potential to the development of novel therapeutic applications.Ministry of Economy of Spain SAF2015-67919-RJunta de Andalucía CS2016-3 P12-BIO1655 PIGE-0440-2019 Pl-0245-2017 PI-0135-2020University of Granada PPJIA2019-0 B-CTS-126-UGR18International Association for the Study of Lung Cancer (IASLC)Spanish Association for Cancer Research (LAB-AECC)PhD "La Caixa Foundation" LCF/BQ/DE15/10360019"Fundacion Benefica Anticancer Santa Candida y San Francisco Javier" predoctoral fellowshipEuropean Commission 837897Spanish Ministry of Education, Culture and Sports FPU fellowship FPU17/00067 FPU17/01258 FPU18/03709PhD FPI-fellowship BES-2013-064596Fundación Científica de la Asociación Española Contra el Cáncer GCB14-2170Fundación Ramon ArecesInstituto de Salud Carlos III-Fondo de Investigación Sanitaria-Fondo Europeo de Desarrollo Regional `Una manera de hacer Europa' (FEDER) PI19/0009

A 3-biomarker 2-point-based risk stratification strategy in acute heart failure

[Abstract] Introduction and Objectives: Most multi-biomarker strategies in acute heart failure (HF) have only measured biomarkers in a single-point time. This study aimed to evaluate the prognostic yielding of NT-proBNP, hsTnT, Cys-C, hs-CRP, GDF15, and GAL-3 in HF patients both at admission and discharge. Methods: We included 830 patients enrolled consecutively in a prospective multicenter registry. Primary outcome was 12-month mortality. The gain in the C-index, calibration, net reclassification improvement (NRI), and integrated discrimination improvement (IDI) was calculated after adding each individual biomarker value or their combination on top of the best clinical model developed in this study (C-index 0.752, 0.715–0.789) and also on top of 4 currently used scores (MAGGIC, GWTG-HF, Redin-SCORE, BCN-bioHF). Results: After 12-month, death occurred in 154 (18.5%) cases. On top of the best clinical model, the addition of NT-proBNP, hs-CRP, and GDF-15 above the respective cutoff point at admission and discharge and their delta during compensation improved the C-index to 0.782 (0.747–0.817), IDI by 5% (p < 0.001), and NRI by 57% (p < 0.001) for 12-month mortality. A 4-risk grading categories for 12-month mortality (11.7, 19.2, 26.7, and 39.4%, respectively; p < 0.001) were obtained using combination of these biomarkers. Conclusion: A model including NT-proBNP, hs-CRP, and GDF-15 measured at admission and discharge afforded a mortality risk prediction greater than our clinical model and also better than the most currently used scores. In addition, this 3-biomarker panel defined 4-risk categories for 12-month mortality.Instituto de Salud Carlos III; RD06-0003-0000Instituto de Salud Carlos III; RD12/0042/000