Ultrafast studies on time-resolved structural dynamics of photodissociating molecules

Tesis inédita de la Universidad Complutense de Madrid, Facultad de Ciencias Químicas, Departamento de Química Física, leída el 06/04/2021El ioduro de metilo (CH3I) se ha convertido en el sistema de referencia para estudios de fotodisociación molecular en la región ultravioleta (UV). Esta molécula presenta tanto dinámicas defotodisociación directa como de predisociación, que conducen a la escisión del enlace C–I, relativamentesimples pero interesante, así como abordable por cálculos teóricos gracias a su estructura de moléculapseudo-diatómica. En concreto, ha sido de interés de diversos experimentadores investigar cómo ladinámica de este sistema simple puede ser modificada a lo largo de la coordenada de reacción, mediantela realización de cambios en su estructura; bien, aumentando el tamaño de la cadena hidrocarbonada,creando ramificaciones, introduciendo insaturaciones o algún átomo sustituyente e incluso ionizando lamolécula para acceder al catión en diferentes estados electrónicos...Methyl iodide (CH3I) has become a reference system for molecular photodissociation studies inthe ultraviolet (UV) region. This molecule presents direct photodissociation as well as predissociationmechanisms, leading to the cleavage of the C−I bond, relatively simple but attractive due to the presenceof conical intersections and non-adiabatic crossing as well as approachable by theoretical calculationsthanks to its pseudo-diatomic structure. In particular, it has been of interest to several experimentershow the photoinduced dynamics of this simple system can be modified along the reaction coordinatethrough changes in the molecular structure; either by increasing the size of the hydrocarbon chain, bycreating branches, introducing unsaturations, or some substituting halogen atoms or ionizing themolecule to get the cation in different electronic states...Fac. de Ciencias QuímicasTRUEunpu

"MOTIVACIÓN EN PROGRAMAS DE ACTIVIDAD FÍSICA EN MUJERES DE LA COMARCA DE LA HOYA DE HUESCA”

El objetivo del estudio fue conocer cuáles son los motivos en la inscripción y adherencia de mujeres adultas en programas de actividad físico-deportiva ofertados por el Servicio de Deportes en la Comarca de la Hoya de Huesca. Para ello se administró la escala de medición de los motivos de actividad física revisada (MPAM-R, Motives for Physical Activity Measure-Revised) de Ryan, Frederick, Lepes, Rubio & Sheldon (1997) y validada en España por Moreno, Cervelló & Martínez (2007) a una muestra de 220 mujeres adultas (62,4 ± 5,86 años) practicantes de dichos programas. Se calcularon los estadísticos descriptivos de la muestra en general y por rango de edades, y también un análisis de correlación de las distintas subescalas. Los resultados muestran que las principales razones para realizar actividades físicas son el fomento de las relaciones sociales así como el disfrute, seguido del fitness o salud y por delante de otras como la competencia y la apariencia, aunque hay variaciones en función de la edad. Palabras clave: motivos, mujeres, actividad física, social, disfrute, salud

Femtosecond XUV induced dynamics of the methyl iodide cation

Ultrashort XUV wavelength-selected pulses obtained with high harmonic generation are used to study the dynamics of molecular cations with state-to-state resolution. We demonstrate this by XUV pump - IR probe experiments on CH3I+ cations and identify both resonant and non-resonant dynamics

Radiative Recombination Processes in Halide Perovskites Observed by Light Emission Voltage Modulated Spectroscopy

The kinetics of light emission in halide perovskite light-emitting diodes (LEDs) and solar cells is composed of a radiative recombination of voltage-injected carriers mediated by additional steps such as carrier trapping, redistribution of injected carriers, and photon recycling that affect the observed luminescence decays. These processes are investigated in high-performance halide perovskite LEDs, with external quantum efficiency (EQE) and luminance values higher than 20% and 80 000 Cd m−2, by measuring the frequency-resolved emitted light with respect to modulated voltage through a new methodology termed light emission voltage modulated spectroscopy (LEVS). The spectra are shown to provide detailed information on at least three different characteristic times. Essentially, new information is obtained with respect to the electrical method of impedance spectroscopy (IS), and overall, LEVS shows promise to capture internal kinetics that are difficult to be discerned by other techniques.Funding for open access charge: CRUE-Universitat Jaume IThe authors thank the financial support by the Ministerio de Ciencia e Innovación of Spain (MICINN) and Agencia Estatal de Investigación AEI/10.13039/501100011033 by projects PID2019-107348GB-100 and STABLE PID2019-107314RB-I00, and by the Generalitat Valenciana with Prometeo Q-Solutions project CIPROM/2021/078

Prosthetic shoulder joint infection by cutibacterium acnes: does rifampin improve prognosis? a retrospective, multicenter, observational study

This retrospective, multicenter observational study aimed to describe the outcomes of surgical and medical treatment of C. acnes-related prosthetic joint infection (PJI) and the potential benefit of rifampin-based therapies. Patients with C. acnes-related PJI who were diagnosed and treated between January 2003 and December 2016 were included. We analyzed 44 patients with C. acnes-related PJI (median age, 67.5 years (IQR, 57.3–75.8)); 75% were men. The majority (61.4%) had late chronic infection according to the Tsukayama classification. All patients received surgical treatment, and most antibiotic regimens (43.2%) included β-lactam. Thirty-four patients (87.17%) were cured; five showed relapse. The final outcome (cure vs. relapse) showed a nonsignificant trend toward higher failure frequency among patients with previous prosthesis (OR: 6.89; 95% CI: 0.80–58.90) or prior surgery and infection (OR: 10.67; 95% IC: 1.08–105.28) in the same joint. Patients treated with clindamycin alone had a higher recurrence rate (40.0% vs. 8.8%). Rifampin treatment did not decrease recurrence in patients treated with β-lactams. Prior prosthesis, surgery, or infection in the same joint might be related to recurrence, and rifampin-based combinations do not seem to improve prognosis. Debridement and implant retention appear a safe option for surgical treatment of early PJI

High-order Harmonic Generation in Thermotropic Liquid Crystals

Thermotropic liquid crystals are versatile optical materials that exhibit a state of matter intermediate between liquids and solids. Their properties can change significantly with temperature, pressure, or other external factors, leading to different phases. The transport properties within these materials in different phases are still largely unexplored and their understanding would enable exciting prospects for innovative technological advancements. High-order harmonic spectroscopy proved to be a powerful spectroscopic tool for investigating the electronic and nuclear dynamics in matter. Here we report the first experimental observation of high-order harmonic generation in thermotropic liquid crystals in two different phase states, nematic and isotropic. We found the harmonic emission in the nematic phase to be strongly dependent on the relative orientation of the driving field polarization with respect to the liquid crystal alignment. Specifically, the harmonic yield has a maximum when the molecules are aligned perpendicularly to the polarization of the incoming radiation. Our results establish the first step for applying high-order harmonic spectroscopy as a tool for resolving ultrafast electron dynamics in liquid crystals with unprecedented temporal and spatial resolution.Comment: The paper is composed by 12 pages including references. Five images are presen

Femtochemistry under scrutiny: Clocking state-resolved channels in the photodissociation of CH3I in the A -band

The following article appeared inThe Journal of Chemical Physics 152.1 (2020): 014304 and may be found at https://doi.org/10.1063/1.5134473Clocking of electronically and vibrationally state-resolved channels of the fast photodissociation of CH3I in the A-band is re-examined in a combined experimental and theoretical study. Experimentally, a femtosecond pump-probe scheme is employed in the modality of resonant probing by resonance enhanced multiphoton ionization (REMPI) of the methyl fragment in different vibrational states and detection through fragment velocity map ion (VMI) imaging as a function of the time delay. We revisit excitation to the center of the A-band at 268 nm and report new results for excitation to the blue of the band center at 243 nm. Theoretically, two approaches have been employed to shed light into the observations: first, a reduced dimensionality 4D nonadiabatic wavepacket calculation using the potential energy surfaces by Xie et al. [J. Phys. Chem. A 104, 1009 (2000)]; and second, a full dimension 9D trajectory surface-hopping calculation on the same potential energy surfaces, including the quantization of vibrational states of the methyl product. In addition, high level ab initio electronic structure calculations have been carried out to describe the CH3 3pz Rydberg state involved in the (2 + 1) REMPI probing process, as a function of the carbon-iodine (C–I) distance. A general qualitative agreement is obtained between experiment and theory, but the effect of methyl vibrational excitation in the umbrella mode on the clocking times is not well reproduced. The theoretical results reveal that no significant effect on the state-resolved appearance times is exerted by the nonadiabatic crossing through the conical intersection present in the first absorption band. The vibrationally state resolved clocking times observed experimentally can be rationalized when the (2 + 1) REMPI probing process is considered. None of the other probing methods applied thus far, i.e., multiphoton ionization photoelectron spectroscopy, soft X-ray innershell photoelectron spectroscopy, VUV single-photon ionization, and XUV core-to-valence transient absorption spectroscopy, have been able to provide quantum state-resolved (vibrational) clocking times. More experiments would be needed to disentangle the fine details in the clocking times and dissociation dynamics arising from the detection of specific quantum-states of the molecular fragmentsM.L.M.-S. acknowledges financial support through a predoctoral contract from Universidad Complutense de Madrid. M.E.C. is grateful to the Spanish MINECO for a contract through Programa de Técnicos de Apoyo a Infraestructuras. This work was financially supported by the Spanish MINECO and MICIU (Grant Nos. CTQ2016-75880-P, FIS2016-77889-R, and PGC2018-096444- B-I00). This research was carried out within the Unidad Asociada Química Física Molecular between the Departamento de Química Física of Universidad Complutense de Madrid and CSIC. The facilities provided by the Center for Ultrasfast Lasers of Universidad Complutense de Madrid are acknowledge

Agronomic performance and remote sensing assessment of organic and mineral fertilization in rice fields

Introduction: Rice heavily relies on nitrogen fertilizers, posing environmental, resource, and geopolitical challenges. This study explores sustainable alternatives like animal manure and remote sensing for resource-efficient rice cultivation. It aims to assess the long-term impact of organic fertilization and remote sensing monitoring on agronomic traits, yield, and nutrition. Methods: A six-year experiment in rice fields evaluated fertilization strategies, including pig slurry (PS) and chicken manure (CM) with mineral fertilizers (MIN), MIN-only, and zero-fertilization. Traits, yield, spectral responses, and nutrient content were measured. Sentinel-2 remote sensing tracked crop development. Results: Cost-effective organic fertilizers (PS and CM) caused a 13% and 15% yield reduction but still doubled zero-fertilization yield. PS reduced nitrogen leaching. Heavy metals in rice grains were present at safe amounts. Organic-fertilized crops showed nitrogen deficiency at the late vegetative stages, affecting yield. Sentinel-2 detected nutrient deficiencies through NDVI. Discussion: Organic fertilizers, especially PS, reduce nitrogen loss, benefiting the environment. However, they come with yield trade-offs and nutrient management challenges that can be managed and balanced with reduced additional mineral applications. Sentinel-2 remote sensing helps manage nutrient deficiencies. In summary, this research favors cost-effective organic fertilizers with improved nutrient management for sustainable rice production.This work was commissioned and funded by the Catalan Ministry of Climate Action, Food and Rural Agenda, by the projects TED2021-131606B-C21 and PLEC2021-007786 of the Spanish Ministry of Economy and Competitiveness and by the CROPDIVA (Climate Resilient Orphan croPs for increased DIVersity in Agriculture) project through the European Union’s Horizon 2020 research and innovation programme under grant agreement No. 101000847. The funders had no role in the study design, data collection and analysis, decision to publish, or manuscript preparation.info:eu-repo/semantics/publishedVersio

Antena de alta eficiencia para localización en entornos hospitalarios

[EN] In this paper, an omni-directional antenna solution is presented to improve the accuracy of indoor location systems, particularly MYSPHERA Bluetooth Real-Time Locating System (RTLS). Emitting antennas with an irregular radiation pattern are not suitable for existing localization techniques due to received signal strength variation in the locators. The approach to an isotropic radiation pattern in the emitting device is what is achieved with presented design using two time-switched antennas with opposing radiation patterns. This solution allows to receive a uniform signal in the locators and increases precision for any technique, frequency or technology used. For MYSPHERA this means more reliability, allowing better processes optimization and increasing efficiency in hospitals.Casanova-Murillo, M.; Cabedo Fabres, M.; Hernández-Cuartero, JF.; Montón-Sánchez, E. (2021). Antena de alta eficiencia para localización en entornos hospitalarios. Íñigo Cuiñas Gómez. 1-3. http://hdl.handle.net/10251/1910651

Immunoregulatory Biomarkers of the Remission Phase in Type 1 Diabetes : miR-30d-5p Modulates PD-1 Expression and Regulatory T Cell Expansion

The partial remission (PR) phase of type 1 diabetes (T1D) is an underexplored period characterized by endogenous insulin production and downmodulated autoimmunity. To comprehend the mechanisms behind this transitory phase and develop precision medicine strategies, biomarker discovery and patient stratification are unmet needs. MicroRNAs (miRNAs) are small RNA molecules that negatively regulate gene expression and modulate several biological processes, functioning as biomarkers for many diseases. Here, we identify and validate a unique miRNA signature during PR in pediatric patients with T1D by employing small RNA sequencing and RT-qPCR. These miRNAs were mainly related to the immune system, metabolism, stress, and apoptosis pathways. The implication in autoimmunity of the most dysregulated miRNA, miR-30d-5p, was evaluated in vivo in the non-obese diabetic mouse. MiR-30d-5p inhibition resulted in increased regulatory T cell percentages in the pancreatic lymph nodes together with a higher expression of CD200. In the spleen, a decrease in PD-1 + T lymphocytes and reduced PDCD1 expression were observed. Moreover, miR-30d-5p inhibition led to an increased islet leukocytic infiltrate and changes in both effector and memory T lymphocytes. In conclusion, the miRNA signature found during PR shows new putative biomarkers and highlights the immunomodulatory role of miR-30d-5p, elucidating the processes driving this phase