Alberto Sols Biomedical Research Institute
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Subphthalocyanine metallo-organic cage as catalytic molecular photoreactor for the functionalization of fullerenes
The dataset that supports the findings of this study are archived in the Universidad Autónoma de Madrid data repository e‐cienciaDatos in https://doi.org/10.21950/STJAKGSubphthalocyanines (SubPcs) are aromatic chromophores with a bowlshaped structure and outstanding optoelectronic properties. The cavity formed by a C3-symmetry trispyridyl-SubPc, Pd(II)-metalloorganic capsule has proved an optimal, shape-complementary space for the complexation of C60. Taking advantage of the intense green light absorption of the SubPc components of the capsule, and their ability to transfer energy/electrons from the excited state, our group has recently described the unprecedented use of SubPc cages as molecular photoreactors to perform photoredox-triggered addition of diphenylamine radicals over encapsulated C60. Unfortunately, the reaction could only be performed using stoichiometric amounts of the cage due to inhibition of the SubPc cavity by the addition compound. Here, we describe the preparation of a more flexible SubPc cage built with a related C1-symmetry trispyridyl-SubPc (C1-SubPc-cage), which could facilitate the exchange between the complexed addition compound and pristine fullerene, thus allowing to use it in catalytic amounts. After assessing the ability of C1-SubPc-cage to host C60, the addition of α-aminoalkyl radicals in the presence of the cage under green light irradiation was tested. Curiously, optimisation of the reaction conditions (using catalytic amounts of C1-SubPc-cage in diluted solutions) rendered a different reaction outcome, that is, a cyclopropanated fullerene, in remarkably high yieldsFinancial support from the Spanish MCIN/AEI/ 10.13039/501100011033 (PID2020-116490GB-I00, PID2020-115801RB-C21), the Comunidad de Madrid and the Spanish State through the Recovery, Transformation and Resilience Plan [“Materiales Disruptivos Bidimensionales (2D)” (MAD2D-CM) (UAM1)-MRR Materiales Avanzados], and the European Union through the Next Generation EU funds is acknowledged. IMDEA Nanociencia acknowledges support from the “Severo Ochoa” Programme for Centres of Excellence in R&D (MINECO, Grant SEV2016-0686
Innovation within Teaching (English<>Spanish) Legal Translation: Hypernymy as a (Sub)Estimated Translation Technique
Globally, the pursuit of translation items is a highly complex, time-consuming issue within international legal settings. It is directly linked to legal systems, with their own lexicon, and meaning. In this article, we seek to show and argue how translators of Law may also resort to a somewhat innovative translation technique, such as hypernymy, to provide a wider lexical equivalent. To achieve our objective, we will generate a list of 18 (North American and Briths) legal items defined by their Spanish translation complexity – parting from our UAM University legal translation students’ outcomes (from a teaching innovation project) – and by their relationship to tribunals and courts decisions. These terms will be looked up (and compared) in both print and online dictionaries, and we will then provide one (or more) hypernym for each of them. By researching and discussing this issue, we will illustrate how helpful hypernyms are in providing innovative translation alternatives‘Errores en los Exámenes de Traducción Directa (Inglés/Árabe-Español) General y Especializada: Análisis, Tipificación e Influencia de la Lengua Inglesa’ (CCG10-UAM/HUM-5665
Plasmonic heating by indium tin oxide nanoparticles: Spectrally enabling decoupled near-infrared theranostics
All-optical theranostic systems are sought after in nanomedicine, since they combine in a single platform therapeutic and diagnostic capabilities. Commonly in these systems the therapeutic and diagnostic/imaging functions are accomplished with plasmonic photothermal agents and luminescent nanoparticles (NPs), respectively. For maximized performance and minimized side effects, these two modalities should be independently activated, i.e., in a decoupled way, using distinct near infrared (NIR) wavelengths: a radiation window wherein photon-tissue interaction is reduced. Yet, to date, a fully decoupled NIR theranostics system is not available. Finding plasmonic NPs working in that range and without spectral overlap with the absorption and emission of state-of-the-art NIR luminescent NPs requires the development of new materials specifically designed for this purpose. To address this limitation, we herein present water-dispersible indium tin oxide (ITO) NPs whose surface plasmon resonance was tuned for exclusive operation in the third biological window (NIR-III, 1500-1800 nm). That leaves available the first and second biological windows, in which diagnostic tools are typically working. Both the microwave-assisted synthesis and the water-transfer protocol were optimized to obtain NPs with maximum light-to-heat conversion capabilities, owing to their small size and reduced aggregation in aqueous media. Proof-of-concept experiments showed that the lack of overlap between the absorption of ITO NPs and the absorption/emission of model near infrared luminescent species (the widely used Nd3+-doped NPs) is an asset when devising an all-optical theranostics platform. The obtained results set the stage for the development of a new generation of high-performance, all-optical theranostic systems with minimized side effectsThis work has been supported by project ref. 2019-T1/ IND-14014 under Talento program and by project S2022/BMD-7403 RENIM-CM, both from Comunidad de Madrid (Spain). N. C-Z. acknowledges financial support from Comunidad de Madrid through both INVESTIGO program, contract number INV/09-PIN1-00013.4/2022, and TALENTO grant ref. 2023-5A/IND-28937. M. Q. acknowledges funding support from CNS2023-145169 SAHNDOCAN, funded by MCIN/AEI/10.13039/501100011033 and EU NextGenerationEU/ PRTR. R. M. is grateful to the Spanish Ministerio de Ciencia e Innovación for support to research through a Ramón y Cajal Fellowship (RYC2021-032913-I). L. V. B. acknowledges support by MCIN/AEI/10.13039/501100011033 and European Union “NextGenerationEU”/PRT through projects PID2020- 118282RA-I00, TED2021-130038A-I00, RYC2021-033818-I, and by Xunta de Galicia under project ED431F 2024/021. JGM acknowledges support by MCIN/AEI/10.13039/501100011033 through project FPU21/03137. A. B. acknowledges funding from Comunidad de Madrid through TALENTO grant ref. 2023-5A/IND-2893
Los niveles plasmáticos elevados de TNF-R1 predicen el desarrollo de eventos isquémicos agudos en pacientes coronarios con diabetes
Objectives: To examine the relationship between inflammatory biomarkers and the occurrence of cardiovascular events in patients with type 2 diabetes mellitus (DM2) and stable coronary artery disease. Methods: A total of 964 patients with stable coronary artery disease were included. Plasma levels of inflammatory markers, including tumour necrosis factor receptors 1 and 2 (TNF-R1 and TNF-R2), growth differentiation factor-15 (GDF-15), soluble suppression of tumorigenicity 2 (sST2), and high-sensitivity C-reactive protein (hsCRP) were measured. The primary endpoint was the development of acute ischaemic events (any type of acute coronary syndrome, stroke, or transient ischaemic attack). Results: There were 232 diabetic patients and 732 non-diabetic patients. Patients with coronary artery disease and DM2 (232, 24%) had higher levels of TNF-R1, TNF-R2, GDF-15, sST2 (P<.001), and hsCRP compared to patients without DM2, indicating a higher inflammatory state. After a median follow-up of 5.39 (2.81-6.92) years, patients with DM2 more frequently developed the primary endpoint (15.9% vs 10.8%; P=.035). Plasma levels of TNF-R1 were independent predictors of the primary endpoint in patients with DM2, along with male gender, triglyceride levels, and the absence of treatment with angiotensin-converting enzyme inhibitors. None of these inflammatory markers predicted the development of this event in non-diabetic patients. Conclusions: Patients with stable coronary artery disease and DM2 exhibit elevated levels of the proinflammatory markers TNF-R1, TNF-R2, GDF-15, and sST2. Moreover, TNF-R1 is an independent predictor of acute ischaemic events only in diabetic patientsEste trabajo ha sido financiado gracias a una Beca de Sociedad Española de Arteriosclerosis y de las siguientes Instituciones: Instituto de Salud Carlos III (ISCIII) y los Fondos FEDER (Fondo Europeo de Desarrollo Regional) de la Unión Europea
(PI20/00487, PI20/0923, PI23/00119); Sociedad Española de Cardiología, Instituto de Salud Carlos III FEDER (Biobanco FJD: RD09/0076/00101). Los financiadores no intervinieron en el diseño del estudio, la recogida y el análisis de datos, la decisión
de publicar o la preparación del manuscrit
Synthesis of azobenzenes from quinone acetals and arylhydrazines
Direct reaction between quinone bisacetals and arylhydrazines gives azobenzenes. The presence of catalytic amounts of cerium ammonium nitrate strongly accelerates the reaction. When the bisacetal has a substituent at the 2,5-cyclohexadiene framework, only one regioisomer is formed. The method represents a simple, mild, and novel synthetic access to differently substituted azocompounds in high to excellent yiel
Structural evolution and bonding within molybdenum-doped tin clusters, MoSn<inf>n</inf> (n = 2 – 15)
Tin clusters can form stable, hollow, cage-like structures which are attractive for the fine-tuning and the creation of new materials via the doping of these clusters with a variety of transition metals. Molybdenum is a particularly interesting possibility for doping due to its role in biological nitrogen fixation and its potential use in the improvement of the Haber–Bosch process. Hence, we address herein a detailed study of the structural, energetic, and electronic properties of molybdenum-doped tin clusters (MoSnn (n = 2 – 15)), using genetic algorithms, density functional theory electronic structure calculations and quantum chemical topology wave function analyses. We considered the last-mentioned type of analyses, because although the properties of metallic nanoclusters depend ultimately on the chemical interactions among their constituent atoms, these studies are scarce. The Quantum Theory of Atoms in Molecules (QTAIM) shows that in MoSnn clusters with n ≥ 6, the Mo atom undergoes electronic charge depletion, as opposed to expectations based on the relative electronegativities of Mo and Sn. This result indicates that the formation of Sn cages significantly increases their electronegativity compared to isolated tin atoms. The Interacting Quantum Atoms energy partition points that the addition of tin atoms to the system strengthen the interaction among themselves, via the covalent contribution of those Sn atoms which are not linked by QTAIM bond paths. Due to the potential use of Mo-doped clusters in nitrogen fixation, we also considered the adsorption of the N2 molecule by selected clusters and we note that the considered MoSnn complexes activate strongly the N [tbnd] N bond. Altogether, this study illustrates how the examination of the evolutional structure and chemical bonding scenarios of bimetallic complexes might provide valuable insights for the design of custom-designed materialsThe authors kindly acknowledge the Spanish MICIU (No. PID2021-122763NB-I00) for financial support. M.G. is grateful to the Spanish MICIU for the predoctoral FPU grant (No. FPU19/02903)
Novel CRISPR-Cas9 iPSC knockouts for PCCA and PCCB genes: Advancing propionic acidemia research
Propionic acidemia (PA) is a rare autosomal recessive metabolic disorder caused by mutations in the PCCA and PCCB genes, which encode subunits of the mitochondrial enzyme propionyl-CoA carboxylase (PCC). This enzyme defciency leads to the accumulation of toxic metabolites, resulting in severe metabolic dysfunction. To create ideal in vitro disease models of PA with isogenic controls and provide a robust platform for therapeutic research, we generated two induced pluripotent stem cell (iPSC) lines with knockout (KO) mutations in the PCCA and PCCB genes using CRISPR-Cas9 gene editing in a healthy control iPSC line. The KO iPS cells were successfully established and characterized, confrming the presence of frameshift insertions and deletions in each target gene, as well as the loss of the corresponding transcript, protein expression, and activity. Additionally, the generated iPSC lines exhibit hallmark characteristics of pluripotency, including the potential to diferentiate into all three germ layers. Our PCCA and PCCB KO iPSC models provide a valuable tool for studying the molecular mechanisms underlying PA and hold potential for advancing new therapeutic approachesThis research was funded by Grant PAF113 from the Propionic Acidemia Foundation; Grant from Fundación Ramón Areces (XX National Call 2020) and by grant PID2022-137238OB-100 funded by MICIU/AEI/https:// doi.org/10.13039/501100011033/ and by ERDF A way of making Europe. EMGT is a PhD student funded by the FPU program (grant FPU22/03244). Centro de Biología Molecular Severo Ochoa receives an institutional grant from Fundación Ramón Areces and is a Severo Ochoa Center of Excellence (MICIN, Award CEX2021-001154-S
Effect of N2 concentration on structural, morphological, and optoelectronic properties of Cu3N films fabricated by RF magnetron sputtering for photodetection applications
Copper nitride (Cu3N) is a promising eco-friendly material for photodetection and photovoltaic absorption. This study focuses on fabricating high-quality Cu3N thin films via reactive radio-frequency magnetron sputtering, using pure N2 and N2/Ar mixture environments, respectively. We investigate how variations in the substrate temperature and the working gas pressure affect absorption capabilities. Phase structure analysis confirms an anti-ReO3 structure with a preferred (100) orientation, and lattice parameters between 0.3810 and 0.3832 nm, with electrical resistivity around 104 Ω cm, indicating a semiconductor character. The films exhibit improved crystalline quality when deposited in pure N2 at 100 °C. Rutherford Backscattering Spectrometry reveals non-stoichiometric films with Cu/N ratios close to 3. The work function showed by the films deposited in N2/Ar is approximately 4.45 eV, while for those deposited in pure N2, the values range from 4.30 to 4.62 eV. Optical properties show a high absorbance and a variable refractive index depending on the deposition conditions. Lastly, the Cu3N films deposited at 100 °C in pure N2 exhibit enhanced photocurrent and photosensitivity of 3.78 × 10−8 A and 9644.9 %, respectively, at 10 V and using AM1.5G as light source. This result underscores the importance of plasma composition as a key factor for obtaining a material with great potential to be applied in such applicationsPartial funding from MEDIDA C17.I2G: CIEMAT. Nuevas tecnolog\u00EDas renovables h\u00EDbridas, Ministerio de Ciencia e Innovaci\u00F3n, Componente 17 \u201CReforma Institucional y Fortalecimiento de las Capacidades del Sistema Nacional de Ciencia e Innovaci\u00F3n\u201D. Medidas del plan de inversiones y reformas para la recuperaci\u00F3n econ\u00F3mica funded by the European Union\u2014Next Generation EU
Infrastructure profile and surrounding land use determine bird-train collision risk in a High-Speed Railway
High-Speed Railways (HSRs) are a growing transportation mode with significant environmental advantages, particularly in reducing carbon emissions. However, their direct impacts on wildlife, especially birds, are not fully understood. This study investigates the factors influencing bird-train collisions and risky bird crossings (crossings through the danger zone, defined as the 8.5-meter area between the railway tracks and the catenary) along a 300 km section of an HSR line in Spain. Using on-board video data, we recorded 675 bird risky crossing events over two years of data collection, totalling 127 journeys and 34,250 km of cumulative travel. Geographic Information System (GIS) data was used to explore three environmental factors affecting risky crossings and potential collision risks: (i) railway height (orography), (ii) surrounding landscape, and (iii) wildlife protected areas. Our findings reveal that certain HSR infrastructure features, such as the presence of tall embankments and surrounding landscape such as nearby open lands (crops and shrubland), significantly increase the frequency of risky crossings. Additionally, we found that species associated with human modified landscapes were particularly prone to these risky crossings, whereas forest birds were rarely observed performing risky crossings. These results highlight that birds’ collision risk is influenced by the biotic changes caused by the HSR. This research offers critical insights into the environmental impacts of HSRs on avian species, offering guidance for future infrastructure development and mitigation strategiesThis study is part of the EU LIFE+ Impacto Cero project (LIFE 12 BIO/ES/000660) focused to the ecology and mortality of birds at highspeed railways. LF, CM, JEM, and JH form part of the REMEDINAL TE-CM research network, funded by the Comunidad de Madrid (P2018/EMT-4338)
Enhancing misinformation countermeasures: A multimodal approach to twitter bot detection
Identifying bots on X (formerly Twitter) is essential for preventing misinformation and ensuring user safety. However, current models face several challenges: (i) the use of outdated techniques and attributes, particularly those trained on older datasets; (ii) reproducibility problems stemming from unique and insufciently detailed methodologies; (iii) shallow analysis depth, with few studies investigating all combinations of feature-based, text-based, and graph-based methods; (iv) a lack of thorough literature reviews to pinpoint efective characteristics for future research. To overcome these gaps, this study proposes a novel multimodal bot detection framework which integrates user profle features, text analysis, and graph-based techniques. Utilizing the recent TwiBot-22 dataset, the model combines semantic text information from user profles and tweets with graph representations of user interactions, including novel relationships like list ownership and all applicable user profle features, encompassing both those previously used in state-of-the-art models and newly introduced features designed to enhance detection accuracy. The study compares the proposed model against existing approaches and demonstrates a signifcant improvement in detection accuracy, exceeding the best-performing models by 5.48%. The research contributes a comprehensive evaluation of feature sets, highlights the advantages of incorporating multiple detection strategies, and identifes key parameters for optimizing bot detection modelsThe research of Quijano-Sanchez was conducted with financial support from the Spanish Ministry of Science and Innovation, grants PID2022-139131NB-I00 & PID2021-122677NB-I0