2D copper-imidazolate framework without thermal treatment as an efficient ORR electrocatalyst for Zn–air batteries

To face unmet energy demands, the search for more stable, low-cost, and scalable electrocatalyst materials is imperative. Within this context, single-atom catalysts (SACs) have drawn considerable attention due to their maximum atom utilization. With this idea in mind, we have synthesized a new ultrathin and water-stable 2D Cu-based metal-organic framework (2DCIFs), which presents a notable electrocatalytic activity for oxygen reduction reaction (ORR) in alkaline media without the need of calcination, which makes the difference when compared to most MOF-based electrocatalysts. The designed MOF-based SAC consists of single-atom sites (isolated and accessible Cu) coordinated to imidazole carboxylic ligands, giving rise to Cu-N4O actives sites confined into a 2D-nanostructured network. This unique structure, along with the ultrathin nature of nanosheets that favors mass transport and electrical conductivity, and the high chemical stability of these 2DCIFs are the key features of the excellent ORR performance, which occurs by a direct four-electron transfer pathway, an onset potential of 0.86 V vs RHE and a maximum current density of 6.4 mA·cm-2. These good catalytic properties of 2DCIFs have allowed their use as efficient air electrodes in alkaline flooded and all-solid-state Zn-air batteries. In the former case, 2DCIFsbased air electrodes presented a specific power density of 91.2 kW·cm-2·kg-1 and a specific capacity of 296.2 A·h·g-1, significantly exceeding the specific capacity values reported previously for other Cu-based catalysts. Besides, the specific capacity increased to 389.1 A·h·g-1 when 2DCIFs were tested in an all-solid-state Zn-air battery

FeN4 active sites generated on dipyridylpyridazine functionalized reduced graphene oxide for high-performance air electrode in a Zn-air battery

The growing global electricity demand requires the development of cost-effective energy conversion and storage systems, integrating inexpensive, eco-friendly, and high-efficiency catalysts. Oxygen reduction reaction (ORR) is considered crucial process to achieve high-power-density fuel cells and Zn-air batteries (ZABs). The latter have attracted the attention of scientific community due to its high theoretical energy density, reliable safety and low-cost. However, several limitations must be overcome, designing ORR catalysts thought versatile and economical synthetic routes. In this sense, the non-noble iron–nitrogen-carbon materials (Fesingle bondNsingle bondC) have been reported as the most potential candidates for attaining superior activity toward ORR in substitution of the high-priced commercial Pt-C catalysts. Herein, Diels-Alder surface adducts based on dipyridylpyridazine units have been created along 2D surface of reduced graphene oxide (rGO) nanosheets for the controlled generation of FeN4 active sites at the edges through successive solvent-free mechanochemical reactions and an additional thermal treatment. The optimized catalyst provided high content of pyridinic-N, graphitic-N and Fe2+ species, contributing to the excellent activity delivered as electrocatalyst for ORR processes. In addition, a flooded ZAB assembled with this material as cathodic/air electrode exhibited excellent specific capacities of 4.94 and 2.77 A·h·g−1 at -1 and -5 mA, respectively, improving the catalytic performance obtained for the 10 wt% Pt-C benchmark electrocatalyst

Impact of SCHOLAR-1 Criteria on Chimeric Antigen Receptor T Cell Therapy Efficacy in Aggressive B Lymphoma: A Real-World GELTAMO/GETH Study

In the pre-chimeric antigen receptor T cell (CAR-T) therapy era, the SCHOLAR-1 study identified a group of patients with refractory aggressive B cell lymphoma (ABCL) with particularly poor prognoses. We recently published our real -world data from Spain, focused on this SCHOLAR-1 refractory group, and compared patients who underwent CAR-T therapy with the previous standard of care. In this study, we found that the efficacy of CAR-T therapy in refractory patients, in terms of progression-free survival (PFS) and overall survival (OS), was superior to that of the treatments available in the pre-CAR-T era. The main objective of these new analyses was to analyze treatment efficacy in terms of response rates and survival for patients with ABCL with or without the SCHOLAR-1 criteria. In addition, we ana-lyzed the prognostic impact of each SCHOLAR-1 criterion independently. Our study aimed to assess the prognostic impact of SCHOLAR-1 criteria on ABCL patients treated with CAR-T therapy in Spain. This multicenter, retrospective, observational study. We included all adult patients treated with commercially available CAR-T cell products and diag-nosed with ABCL different from primary mediastinal large B cell lymphoma between February 2019 and July 2022. Patients meeting any SCHOLAR-1 criteria (progressive disease as the best response to any line of therapy, stable dis-ease as the best response to >4 cycles of first-line therapy or >2 cycles of later-line therapy, or relapse at <12 months after autologous stem cell transplantation [auto-SCT]) in the line of treatment before CAR-T therapy (SCHOLAR-1 group) were compared with those not meeting any of these criteria (non-SCHOLAR-1 group). To analyze the prognos-tic impact of individual SCHOLAR-1 criteria, all the patients who met any of the SCHOLAR-1 criteria at any time were included to assess whether these criteria have the same prognostic impact in the CAR-T era. In addition, patients were grouped according to whether they were refractory to the first line of treatment, refractory to the last line of treatment, or relapsed early after auto-SCT. The PFS and OS were calculated from the time of appearance of the SCHOLAR-1 refractoriness criteria. Of 329 patients treated with CAR-T (169 with axi-cel and 160 with tisa-cel), 52 were in the non-SCHOLAR-1 group and 277 were in the SCHOLAR-1 group. We found significantly better outcomes in the non-SCHOLAR-1 patients compared with the SCHOLAR-1 patients (median PFS of 12.2 and 3.3 months, respectively; P = .009). In addition, axi-cel showed better results in terms of efficacy than tisa-cel for both the non SCHOLAR-1 group (hazard ratio [HR] for PFS, 2.7 [95% confidence interval (CI), 1.1 to 6.7; P = .028]; HR for OS, 7.1 [95% CI, 1.5 to 34.6; P = .015]) and SCHOLAR-1 group (HR for PFS, 1.8 [95% CI, 1.3 to 2.5; P < .001]; HR for OS, 1.8 [95% CI, 1.2 to 2.6; P = .002]), but also significantly more toxicity. Finally, separately analyzing the prognostic impact of each SCHOLAR-1 criterion revealed that refractoriness to the last line of treatment was the variable with the most significant impact on survival. In conclusion, SCHOLAR-1 refractoriness criteria notably influence the efficacy of CAR-T therapy. In our experience, axi-cel showed better efficacy than tisa-cel for both SCHOLAR-1 and non-SCHOLAR-1 patients. Refractoriness to the last line of treatment was the variable with the most significant impact on survival in the CAR-T therapy era.(c) 2023 The American Society for Transplantation and Cellular Therapy. Published by Elsevier Inc

Efficacy of clozapine versus standard treatment in adult individuals with intellectual disability and treatment-resistant psychosis (CLOZAID): study protocol of a multicenter randomized clinical trial

BackgroundIntellectual disability (ID) affects approximately 1% of the worldwide population and individuals with ID have a higher comorbidity with mental illness, and specifically psychotic disorders. Unfortunately, among individuals with ID, limited research has been conducted since ID individuals are usually excluded from mental illness epidemiological studies and clinical trials. Here we perform a clinical trial to investigate the effectiveness of clozapine in the treatment of resistant psychosis in individuals with ID. The article highlights the complexity of diagnosing and treating psychopathological alterations associated with ID and advocates for more rigorous research in this field.MethodsA Phase IIB, open-label, randomized, multicenter clinical trial (NCT04529226) is currently ongoing to assess the efficacy of oral clozapine in individuals diagnosed with ID and suffering from treatment-resistant psychosis. We aim to recruit one-hundred and fourteen individuals (N=114) with ID and resistant psychosis, who will be randomized to TAU (treatment as usual) and treatment-with-clozapine conditions. As secondary outcomes, changes in other clinical scales (PANSS and SANS) and the improvement in functionality, assessed through changes in the Euro-QoL-5D-5L were assessed. The main outcome variables will be analyzed using generalized linear mixed models (GLMM), assessing the effects of status variable (TAU vs. Clozapine), time, and the interaction between them.DiscussionThe treatment of resistant psychosis among ID individuals must be directed by empirically supported research. CLOZAID clinical trial may provide relevant information about clinical guidelines to optimally treat adults with ID and treatment-resistant psychosis and the benefits and risks of an early use of clozapine in this underrepresented population in clinical trials.Trial registrationClinicaltrials.gov: NCT04529226. EudraCT: 2020-000091-37

Influence of the synthesis route on the electrocatalytic performance for ORR of citrate-stabilized gold nanoparticles

Embargado hasta 18/09/2024Citrate-stabilized gold nanoparticles (AuNPs) were synthesized by two different citrate-based reduction methods, namely a one-pot wet chemical synthesis (Turkevich method) and seed-mediated growth (Bastús method). Although both types of AuNPs produce similar surface plasmon resonance bands and have a similar particle size and shape, the NPs obtained by the Turkevich method show significantly higher crystallinity. Static and dynamic electrochemical analysis using both types of AuNPs for the oxygen reduction reaction (ORR), under alkaline conditions, confirmed the significant influence of the synthesis route on the resulting onset potentials and maximum intensities in ORR electrocatalysis. These results were attributed to the higher percentage of Au(100) facets and the greater number of active sites on citrate-stabilized AuNPs obtained by the Turkevich method. Underpotential deposition of lead and electrochemical active surface area (ECSA) analysis further confirmed the importance of the crystalline facets in the performance of the AuNPs as electrocatalysts. This study demonstrates the influence of the synthesis route on the electrocatalytic activity of AuNPs, despite using the same starting reagents

Human Hemoglobin-Based Zinc–Air Battery in a Neutral Electrolyte

Embargado hasta 01/10/2024The use of human hemoglobin (Hb) as a catalytic component of the air electrode in a primary zinc–air battery with a neutral electrolyte has been investigated. Three different electrode modifications, using the drop-casting method, with Hb and Nafion were first tested in a three-electrode cell, obtaining the best oxygen electroreduction (ORR) performance and long-term stability with a Hb plus Nafion (Hb–Nafion)-modified electrode. The latter Hb–Nafion-based air electrode provided a higher specific capacity and discharge time than the opposite order (Nafion–Hb)

Photo-induced and electrochemical applications of carbon based-nanoparticles from spent coffee grounds

Embargado hasta 04/04/2025The interest of the scientific community toward carbon-based nanostructures is justified by the wide range of applications of such multifaceted structures. In the present work, carbon nanoparticles (CNPs) were synthesized, in mild conditions, by using spent coffee grounds as the carbon source. Green-emitting CNPs of about 40 nm were obtained, and they were characterized by X-ray photoelectron spectroscopy, energy-dispersive X-ray spectroscopy, fluorescence spectroscopy, and Fourier transform infrared spectroscopy, highlighting that they are naturally doped with N, K, Mg, and P. Such intrinsic doping promotes the characteristic green emission; furthermore, the N- and P-doping prompted us to evaluate their ability to photoproduce 1O2 for PDT applications. The presence of heteroatoms in the CNP structure was also used to electrochemically promote the oxygen reduction reaction and hydrogen evolution reaction catalysis

Ruxolitinib in refractory acute and chronic graft-versus-host disease: a multicenter survey study

Graft-versus-host disease is the main cause of morbidity and mortality after allogeneic hematopoietic stem cell transplantation. First-line treatment is based on the use of high doses of corticosteroids. Unfortunately, second-line treatment for both acute and chronic graft-versus-host disease, remains a challenge. Ruxolitinib has been shown as an effective and safe treatment option for these patients. Seventy-nine patients received ruxolitinib and were evaluated in this retrospective and multicenter study. Twenty-three patients received ruxolitinib for refractory acute graft-versus-host disease after a median of 3 (range 1–5) previous lines of therapy. Overall response rate was 69.5% (16/23) which was obtained after a median of 2 weeks of treatment, and 21.7% (5/23) reached complete remission. Fifty-six patients were evaluated for refractory chronic graft-versus-host disease. The median number of previous lines of therapy was 3 (range 1–10). Overall response rate was 57.1% (32/56) with 3.5% (2/56) obtaining complete remission after a median of 4 weeks. Tapering of corticosteroids was possible in both acute (17/23, 73%) and chronic graft-versus-host disease (32/56, 57.1%) groups. Overall survival was 47% (CI: 23–67%) at 6 months for patients with aGVHD (62 vs 28% in responders vs non-responders) and 81% (CI: 63–89%) at 1 year for patients with cGVHD (83 vs 76% in responders vs non-responders). Ruxolitinib in the real life setting is an effective and safe treatment option for GVHD, with an ORR of 69.5% and 57.1% for refractory acute and chronic graft-versus-host disease, respectively, in heavily pretreated patients

Intravenous metoprolol during ongoing STEMI ameliorates markers of ischemic injury: a METOCARD-CNIC trial electrocardiographic study

Besides its protective effect against neutrophil-mediated injury at reperfusion, intravenous (IV) metoprolol was recently shown to reduce the progression of ischemic injury in a pig model of ST-segment elevation myocardial infarction (STEMI). Here, we tested the hypothesis that IV metoprolol administration in humans with ongoing STEMI blunts the time‑dependent progression of ischemic injury assessed by serial electrocardiogram (ECG) evaluations before reperfusion. The METOCARD-CNIC trial randomized 270 anterior STEMI patients to IV metoprolol or control before reperfusion by percutaneous coronary intervention (PCI). In 139 patients (69 IV metoprolol, 70 controls), two ECGs were available (ECG-1 before randomization, ECG-2 pre-PCI). Between-group ECG differences were analyzed using univariate and multivariate regression models. No significant between-group differences were observed on ECG-1. On ECG-2, patients who received IV metoprolol had a narrower QRS than those in the control group (84 ms vs. 90 ms, p = 0.029), a lower prevalence of QRS distortion (10% vs. 26%, p = 0.017), and a lower sum of anterior and total ST-segment elevation (10.1 mm vs. 13.6 mm, p = 0.014 and 10.4 mm vs. 14.0 mm, p = 0.015, respectively). Adjusted analysis revealed similar results. Significant associations were observed between ECG-2 variables and cardiac magnetic resonance imaging measurements (extent of myocardial edema, infarct size, microvascular obstruction, and left-ventricular ejection fraction) after STEMI. In summary, IV metoprolol administration before reperfusion ameliorates ECG markers of myocardial ischemia in anterior STEMI patients. These data confirm that IV metoprolol is able to reduce ischemic injury and highlight the ability of ECG analysis to provide relevant real-time information on the effect of cardioprotective therapies before reperfusion.Spanish Ministry of Science and Innovation (RETOS2019-107332RB-I00)Instituto de Salud Carlos III (PI19/01704)CNIC (Translational Grant 01-2009)Spanish National Ministry of Health and Social Policy (EC10-042)Mutua Madrileña Foundation (AP8695-2011)Severo Ochoa Center of Excellence (SEV-2015–0505)12.416 JCR (2021) Q1, 13/143 Cardiac & Cardiovascular Systems1.615 SJR (2021) Q1, 49/356 Cardiology and Cardiovascular MedicineNo data IDR 2020UE

Surface Diels–Alder adducts on multilayer graphene for the generation of edge-enriched single-atom FeN4 sites for ORR and OER electrocatalysis

Embargado hasta 15/02/2023The assembly of atomically dispersed iron–nitrogen (FeN4) sites into graphitic structures is a promising approach for sustainable production of bifunctional electrocatalysts for the oxygen electroreduction (ORR) and oxygen evolution (OER) reactions. In addition, single-atom FeN4 sites at the edges of carbon substrates provide higher electrocatalytic performance than those in plane. Unfortunately, the conventional high-temperature pyrolysis method does not allow the generation of edge-enriched FeN4 single-atom sites. Herein, a novel low-temperature and solvent-free mechanochemical synthesis based on the use of dipyridylpyridazine (dppz) functionalized multilayer graphene as a starting material is proposed for precisely engineered location of these FeN4 active sites at the edges. After careful characterization of these dppz-based materials, the ORR and OER electrocatalytic performance was investigated, demonstrating the efficient formation of FeN4 sites at the edges as well as their excellent bifunctional behavior for the ORR and OER. This work paves the way for the development of sustainable approaches for the generation of edge-enriched FeN4 single atom sites on multilayer graphene structures