Ferromagnetic supramolecular metal-organic frameworks for active capture and magnetic sensing of emerging drug pollutants

Capture and sensing of emerging pollutants is one of the increasing environmental concerns due to the adverse ecological and human health effects. Here, we report the synthesis of a supramolecular metal-organic framework (SMOF) [CrCu6(m-H2O)6(m3-OH)6(m-adeninato-kN33:kN9)6](SO4)1.5 which is able to capture anionic drugs and exhibits magnetic properties useful for sensing purposes. The features of the nucleobase decorated CrCu6 building block allow the incorporation of up to 9 drug molecules (i.e., ibuprofen and naproxen in this work) per heptameric entity. In addition, we provide a simple way to quantify the incorporated number of drug molecules through a magnetic sustentation experiment in which the field required to keep the particles attached to the electromagnet pole is linearly related to the total mass of the anionic counterion. In this way, it also provides an easy way to determine the amount of entrapped drug molecules, making this SMOF a promising candidate for environmental remediation technologies.This work has been funded by the Universidad del País Vasco/Euskal Herriko Unibertsitatea (GIU17/50), the Gobierno Vasco/Eusko Jaurlaritza (PIBA18/14; IT1291-19), the Ministerio de Economía y Competitividad (MAT2016-75883-C2-1-P), the Ministerio de Ciencia e Innovación (PID2019-108028GB-C21), and FEDER funds. Technical and human support provided by SGIker (UPV/EHU, MICINN, GV/EJ, and ESF) is also acknowledged

Thermochemical CO2 reduction catalyzed by homometallic and heterometallic nanoparticles generated from the thermolysis o supramolecularly assembled porous metal-adenine precursors

A family of unprecedented supramolecularly assembled porous metal–organic compounds (SMOFs), based on [Cu6M(μ-adeninato)6(μ3-OH)6(μ-H2O)6]2+ cations (MII: Cu, Co, Ni, and Zn) and different dicarboxylate anions (fumarate, benzoate, and naphthalene-2,6-dicarboxylate), have been employed as precursors of catalysts for the thermocatalytic reduction of CO2. The selected metal–organic cation allows us to tune the composition of the SMOFs and, therefore, the features and performance of the final homometallic and bimetallic catalysts. These catalysts were obtained by thermolysis at 600 °C under a N2 atmosphere and consist of big metal particles (10–20 μm) placed on the surface of the carbonaceous matrix and very tiny metal aggregates (<10 nm) within this carbonaceous matrix. The latter are the most active catalytic sites for the CO2 thermocatalytic reduction. The amount of this carbonaceous matrix correlates with the organic content present in the metal–organic precursor. In this sense, CO2 thermocatalytic reduction experiments performed over the homometallic, copper only, catalysts with different carbon contents indicate that above a certain value, the increase of the carbonaceous matrix reduces the overall performance by encapsulating the nanoparticles within this matrix and isolating them from interacting with CO2. In fact, the best performing homometallic catalyst is that obtained from the precursor containing a small fumarate counterion. On the other hand, the structural features of these precursors also provide a facile route to work with a solid solution of nanoparticles as many of these metal–organic compounds can replace up to 1/7 of the copper atoms by zinc, cobalt, or nickel. Among these heterometallic catalysts, the best performing one is that of copper and zinc, which provides the higher conversion and selectivity toward CO. XPS spectroscopy and EDX mappings of the latter catalyst clearly indicate the presence of Cu1–xZnx nanoparticles covered by small ZnO aggregates that provide a better CO2 adsorption and easier CO release sites.Eusko Jaurlaritza/Gobierno Vasco (IT1291-19; IT1722-22 and Investigo program for S.M.G. funded by the European Union-Next Generation EU). Universidad del País Vasco/Euskal Herriko Unibertsitatea (predoctoral fellowship for J.P.C. 17/051), Ministerio de Ciencia e Innovación (project PID2019-108028GB-C21 funded by MCIN/AEI/10.13039/501100011033; PID2022-138968NB-C22 funded by MCIN/AEI/10.13039/501100011033/FEDER/FEDER, and TED2021-129810B-C22 funded by MCIN/AEI/10.13039/501100011033 and by the European Union NextGeneration EU/PRTR)

An in solution adsorption characterization technique based on the response to an external magnetic field of porous paramagnetic materials: application on supramolecular metal–adenine frameworks containing heterometallic heptameric clusters

Herein we explore the opportunities arising from combining magnetic properties and porosity in metal–organic materials. In this sense, we have prepared an adenine based homometallic wheel-shaped heptameric [Cu7(μ-adeninato)6(μ3-OH)6(μ-OH2)4]2+ entity containing two metal coordination environments: CuO6 at the core of the wheel with an unusually modest Jahn–Teller distortion and six peripheral CuN2O4 with a more pronounced elongation. The difference in the coordination environments of this compound facilitates the selective replacement of the central metal position by other metal centers (ZnII, NiII, CoII and CrIII) and boosts the magnetic properties of the homometallic heptameric entity. The nature of the central metal modulates the complex net of ferro- and antiferromagnetic superexchange pathways within the heptameric entity to tune the total spin (ST = 3 (Cu6Zn), 5/2 (Cu6Cu), 2 (Cu6Ni), 3/2 (Cu6Co), and 9/2 (Cu6Cr)). No evidence of single-molecule magnet behavior has been observed at 2 K, but at room temperature, where these compounds are still in the paramagnetic regime, the attraction force exerted by an external magnetic field (H) on particles immersed in a liquid is enough to keep them attached to an electromagnet pole. The 4S(S + 1) value of the central metal follows a linear dependence with respect to the 1/[H·∇(H)] value at which the particles are detached from the pole of the electromagnet. There is also a linear dependence of the H·∇(H) term with respect to the adsorbate mass incorporated inside the pores of the paramagnetic adsorbent which has allowed performing straightforward sorption selectivity experiments on Cu6Cu directly in solution, which are based on a property of the adsorbent and not as usually based on an indirect assessment of the adsorbate remaining in solution.Eusko Jaurlaritza/Gobierno Vasco (IT1291-19; IT1722-22; ELKARTEK program KK-2022/00032), Ministerio de Universidades and the European Union-Next Generation EU (marsa21/52, R. P. A.), Ministerio de Ciencia e Innovación (PID2019-108028GB-C21). SGIker (UPV/EHU, MICINN, GV/EJ, ESF). ELKARTEK program KK-2022/0003

Isoreticular chemistry and applications of supramolecularly assembled copper−adenine porous materials

The useful concepts of reticular chemistry, rigid and predictable metal nodes together with strong and manageable covalent interactions between metal centers and organic linkers, have made the so-called metal–organic frameworks (MOFs) a flourishing area of enormous applicability. In this work, the extension of similar strategies to supramolecularly assembled metal–organic materials has allowed us to obtain a family of isoreticular compounds of the general formula [Cu7(μ-adeninato-κN3:κN9)6(μ3-OH)6(μ-OH2)6](OOC-R-COO)·nH2O (R: ethylene-, acetylene-, naphthalene-, or biphenyl-group) in which the rigid copper–adeninato entities and the organic dicarboxylate anions are held together not by covalent interactions but by a robust and flexible network of synergic hydrogen bonds and π–π stacking interactions based on well-known supramolecular synthons (SMOFs). All compounds are isoreticular, highly insoluble, and water-stable and show a porous crystalline structure with a pcu topology containing a two-dimensional (2D) network of channels, whose dimensions and degree of porosity of the supramolecular network are tailored by the length of the dicarboxylate anion. The partial loss of the crystallization water molecules upon removal from the mother liquor produces a shrinkage of the unit cell and porosity, which leads to a color change of the compounds (from blue to olive green) if complete dehydration is achieved by means of gentle heating or vacuuming. However, the supramolecular network of noncovalent interactions is robust and flexible enough to reverse to the expanded unit cell and color after exposure to a humid atmosphere. This humidity-driven breathing behavior has been used to design a sensor in which the electrical resistance varies reversibly with the degree of humidity, very similar to the water vapor adsorption isotherm of the SMOF. The in-solution adsorption properties were explored for the uptake and release of the widely employed 5-fluorouracil, 4-aminosalycilic acid, 5-aminosalycilic acid, and allopurinol drugs. In addition, cytotoxicity activity assays were completed for the pristine and 5-fluorouracil-loaded samples.Basque Goverment (IT1722-22 and ELKARTEK KK-2022/00032) . Spanish Ministry of Science and Innovation (TED2021-129810B-C22 financed by MCIN/AEI/10.13039/501100011033 and by the European Union Next Generation EU/PRTR, and the PID2019-108028GB-C21 project funded by MCIN/AEI/10.13039/501100011033). Basque Government and the European Union Next GenerationEU (Investigo Program 2022-46)

Health literacy and health outcomes in very old patients with heart failure

INTRODUCTION AND OBJECTIVES: Health literacy (HL) has been associated with lower mortality in heart failure (HF). However, the results of previous studies may not be generalizable because the research was conducted in relatively young and highly-educated patients in United States settings. This study assessed the association of HL with disease knowledge, self-care, and all-cause mortality among very old patients, with a very low educational level. METHODS: This prospective study was performed in 556 patients (mean age, 85 years), with high comorbidity, admitted for HF to the geriatric acute-care unit of 6 hospitals in Spain. About 74% of patients had less than primary education and 71% had preserved systolic function. Health literacy was assessed with the Short Assessment of Health Literacy for Spanish-speaking Adults questionnaire, knowledge of HF with the DeWalt questionnaire, and HF self-care with the European Heart Failure Self-Care Behaviour Scale. RESULTS: Disease knowledge progressively increased with HL; compared with being in the lowest (worse) tertile of HL, the multivariable beta coefficient (95%CI) of the HF knowledge score was 0.60 (0.01-1.19) in the second tertile and 0.87 (0.24-1.50) in the highest tertile, P-trend = .008. However, no association was found between HL and HF self-care. During the 12 months of follow-up, there were 189 deaths. Compared with being in the lowest tertile of HL, the multivariable HR (95%CI) of mortality was 0.84 (0.56-1.27) in the second tertile and 0.99 (0.65-1.51) in the highest tertile, P-trend = .969. CONCLUSIONS: No association was found between HL and 12-month mortality. This could be partly due to the lack of a link between HL and self-care

Wikipedia como herramienta de aprendizaje en el EEES en la docencia de la lengua española en la educación primaria

Memoria ID12-0109. Ayudas de la Universidad de Salamanca para la innovación docente, curso 2012-2013

Prevalence and Clinical Characteristics of Children With Nonsevere Tuberculosis in Spain

Background: To assess the prevalence and characteristics of nonsevere TB among children in Spain. It has been recently demonstrated that these children can be treated with a 4-month regimen instead of the classical 6-month treatment regimen, with the same effectivity and outcomes, decreasing toxicity and improving adherence. Methods: We conducted a retrospective cohort study in a cohort of children ≤16 years of age with TB. Nonsevere TB cases included smear-negative children with respiratory TB confined to 1 lobe, with no significant airway obstruction, no complex pleural effusion, no cavities and no signs of miliary disease, or with peripheral lymph-node disease. The remaining children were considered to have severe TB. We estimated the prevalence of nonsevere TB and compared the clinical characteristics and outcomes between children with nonsevere and severe TB. Results: A total of 780 patients were included [46.9% males, median age 5.5 years (IQR: 2.6–11.1)], 477 (61.1%) of whom had nonsevere TB. Nonsevere TB was less frequent in children 14 years of age (35% vs 65%; P = 0.002), mostly diagnosed in contact tracing studies (60.4% vs 29.2%; P < 0.001) and more frequently asymptomatic (38.3% vs 17.7%; P < 0.001). TB confirmation in nonsevere disease was less frequent by culture (27.0% vs 57.1%; P < 0.001) and by molecular tests (18.2% vs 48.8%; P < 0.001). Sequelae were less frequent in children with nonsevere disease (1.7 vs 5.4%; P < 0.001). No child with nonsevere disease died. Conclusions: Two-thirds of children had nonsevere TB, mostly with benign clinical presentation and negative microbiologic results. In low-burden countries, most children with TB might benefit from short-course regimens.Peer reviewe

Rationale and methods of the multicenter randomised trial of a heart failure management programme among geriatric patients (HF-Geriatrics)

<p>Abstract</p> <p>Background</p> <p>Disease management programmes (DMPs) have been shown to reduce hospital readmissions and mortality in adults with heart failure (HF), but their effectiveness in elderly patients or in those with major comorbidity is unknown. The Multicenter Randomised Trial of a Heart Failure Management Programme among Geriatric Patients (HF-Geriatrics) assesses the effectiveness of a DMP in elderly patients with HF and major comorbidity.</p> <p>Methods/Design</p> <p>Clinical trial in 700 patients aged ≥ 75 years admitted with a primary diagnosis of HF in the acute care unit of eight geriatric services in Spain. Each patient should meet at least one of the following comorbidty criteria: Charlson index ≥ 3, dependence in ≥ 2 activities of daily living, treatment with ≥ 5 drugs, active treatment for ≥ 3 diseases, recent emergency hospitalization, severe visual or hearing loss, cognitive impairment, Parkinson's disease, diabetes mellitus, chronic obstructive pulmonary disease (COPD), anaemia, or constitutional syndrome. Half of the patients will be randomly assigned to a 1-year DMP led by a case manager and the other half to usual care. The DMP consists of an educational programme for patients and caregivers on the management of HF, COPD (knowledge of the disease, smoking cessation, immunizations, use of inhaled medication, recognition of exacerbations), diabetes (knowledge of the disease, symptoms of hyperglycaemia and hypoglycaemia, self-adjustment of insulin, foot care) and depression (knowledge of the disease, diagnosis and treatment). It also includes close monitoring of the symptoms of decompensation and optimisation of treatment compliance. The main outcome variables are quality of life, hospital readmissions, and overall mortality during a 12-month follow-up.</p> <p>Discussion</p> <p>The physiological changes, lower life expectancy, comorbidity and low health literacy associated with aging may influence the effectiveness of DMPs in HF. The HF-Geriatrics study will provide direct evidence on the effect of a DMP in elderly patients with HF and high comorbidty, and will reduce the need to extrapolate the results of clinical trials in adults to elderly patients.</p> <p>Trial registration</p> <p>(ClinicalTrials.gov number, <a href="http://www.clinicaltrials.gov/ct2/show/NCT01076465">NCT01076465</a>).</p

International consensus definition of low anterior resection syndrome

BACKGROUND: Low anterior resection syndrome is pragmatically defined as disordered bowel function after rectal resection leading to a detriment in quality of life. This broad characterization does not allow for precise estimates of prevalence. The low anterior resection syndrome score was designed as a simple tool for clinical evaluation of low anterior resection syndrome. Although the low anterior resection syndrome score has good clinical utility, it may not capture all important aspects that patients may experience. OBJECTIVE: The aim of this collaboration was to develop an international consensus definition of low anterior resection syndrome that encompasses all aspects of the condition and is informed by all stakeholders. DESIGN: This international patient-provider initiative used an online Delphi survey, regional patient consultation meetings, and an international consensus meeting. PARTICIPANTS: Three expert groups participated: patients, surgeons, and other health professionals from 5 regions (Australasia, Denmark, Spain, Great Britain and Ireland, and North America) and in 3 languages (English, Spanish, and Danish). MAIN OUTCOME MEASURE: The primary outcome measured was the priorities for the definition of low anterior resection syndrome. RESULTS: Three hundred twenty-five participants (156 patients) registered. The response rates for successive rounds of the Delphi survey were 86%, 96%, and 99%. Eighteen priorities emerged from the Delphi survey. Patient consultation and consensus meetings refined these priorities to 8 symptoms and 8 consequences that capture essential aspects of the syndrome. LIMITATIONS: Sampling bias may have been present, in particular, in the patient panel because social media was used extensively in recruitment. There was also dominance of the surgical panel at the final consensus meeting despite attempts to mitigate this. CONCLUSIONS: This is the first definition of low anterior resection syndrome developed with direct input from a large international patient panel. The involvement of patients in all phases has ensured that the definition presented encompasses the vital aspects of the patient experience of low anterior resection syndrome. The novel separation of symptoms and consequences may enable greater sensitivity to detect changes in low anterior resection syndrome over time and with intervention

A922 Sequential measurement of 1 hour creatinine clearance (1-CRCL) in critically ill patients at risk of acute kidney injury (AKI)

Meeting abstrac