On-Surface Covalent Synthesis of Carbon Nanomaterials by Harnessing Carbon gem-Polyhalides.

The design of innovative carbon-based nanostructures stands at the forefront of both chemistry and materials science. In this context, π-conjugated compounds are of great interest due to their impact in a variety of fields, including optoelectronics, spintronics, energy storage, sensing and catalysis. Despite extensive research efforts, substantial knowledge gaps persist in the synthesis and characterization of new π-conjugated compounds with potential implications for science and technology. On-surface synthesis has emerged as a powerful discipline to overcome limitations associated with conventional solution chemistry methods, offering advanced tools to characterize the resulting nanomaterials. This review specifically highlights recent achievements in the utilization of molecular precursors incorporating carbon geminal (gem)-polyhalides as functional groups to guide the formation of π-conjugated 0D species, as well as 1D, quasi-1D π-conjugated polymers, and 2D nanoarchitectures. By delving into reaction pathways, novel structural designs, and the electronic, magnetic, and topological features of the resulting products, the review provides fundamental insights for a new generation of π-conjugated materials.

Controlling On-Surface Photoactivity: The Impact of π-Conjugation in Anhydride-Functionalized Molecules on a Semiconductor Surface.

On-surface synthesis has become a prominent method for growing low-dimensional carbon-based nanomaterials on metal surfaces. However, the necessity of decoupling organic nanostructures from metal substrates to exploit their properties requires either transfer methods or new strategies to perform reactions directly on inert surfaces. The use of on-surface light-induced reactions directly on semiconductor/insulating surfaces represents an alternative approach to address these challenges. Here, exploring the photochemical activity of different organic molecules on a SnSe semiconductor surface under ultra-high vacuum, we present a novel on-surface light-induced reaction. The selective photodissociation of the anhydride group is observed, releasing CO and CO2. Moreover, we rationalize the relationship between the photochemical activity and the π-conjugation of the molecular core. The different experimental behaviour of two model anhydrides was elucidated by theoretical calculations, showing how the molecular structure influences the distribution of the excited states. Our findings open new pathways for on-surface synthesis directly on technologically relevant substrates.

Diseño de un panel de indicadores para programas de optimización del uso de antimicrobianos en los Servicios de Urgencias / Design of a panel of indicators for antibiotic stewardship programs in the Emergency Department

Objetivo: desarrollar un panel de indicadores para monitorizar la actividad de los programas de optimización del uso de antimicrobianos en los servicios de urgencias. Métodos: un grupo multidisciplinar formado por expertos en el manejo de la infección en urgencias y en la implantación de programas de optimización de uso de antimicrobianos (PROA) evaluó una propuesta de indicadores utilizando una metodología Delphi modificada. En una primera ronda, cada uno de los expertos clasificó la relevancia de cada indicador propuesto en 2 dimensiones (repercusión asistencial y facilidad de implantación) y 2 atributos (nivel de priorización y periodicidad de medida). La segunda ronda se realizó a partir del cuestionario modificado de acuerdo con las sugerencias planteadas y nuevos indicadores sugeridos por los participantes. Los expertos efectuaron modificaciones en el orden de priorización y calificaron los nuevos indicadores propuestos de la misma manera que en la primera ronda. Resultados: se propusieron un total de 61 potenciales indicadores divididos en 4 grupos: indicadores de consumo, microbiológicos, de proceso y de resultado. Tras el análisis de las puntuaciones y los comentarios realizados en la primera ronda, 31 indicadores fueron clasificados como de alta prioridad, 25 de prioridad intermedia y 5 de baja prioridad. Además se generaron 19 nuevos indicadores. Tras la segunda ronda, se mantuvieron los 61 indicadores inicialmente propuestos y adicionalmente se incorporaron 18 nuevos: 11 como de alta prioridad, 3 como de intermedia y 4 como de baja prioridad. Conclusiones: los expertos consensuaron un panel de indicadores PROA adaptado a los servicios de urgencias priorizados por nivel de relevancia como un elemento de ayuda para el desarrollo de estos programas, que contribuirá a monitorizar la adecuación del uso de antimicrobianos en estas unidades.(AU)

Objective: To develop a panel of indicators to monitor antimicrobial stewardship programs activity in the emergency department. Methods: A multidisciplinary group consisting of experts in the management of infection in emergency departments and the implementation of antimicrobial stewardship programs (ASP) evaluated a proposal of indicators using a modified Delphi methodology. In the first round, each expert classified the relevance of each proposed indicators in two dimensions (healthcare impact and ease of implementation) and two attributes (prioritization level and frequency). The second round was conducted based on the modified questionnaire according to the suggestions raised and new indicators suggested. Experts modified the prioritization order and rated the new indicators in the same manner as in the first round. Results: 61 potential indicators divided into four groups were proposed: consumption indicators, microbiological indicators, process indicators, and outcome indicators. After analyzing the scores and comments from the first round, 31 indicators were classified as high priority, 25 as intermediate priority, and 5 as low priority. Moreover, 18 new indicators were generated. Following the second round, all 61 initially proposed indicators were retained, and 18 new indicators were incorporated: 11 classified as high priority, 3 as intermediate priority, and 4 as low priority. Conclusions: The experts agreed on a panel of ASP indicators adapted to the emergency services prioritized by level of relevance. This is as a helpful tool for the development of these programs and will contribute to monitoring the appropriateness of the use of antimicrobials in these units.(AU)

Design of a panel of indicators for antibiotic stewardship programs in the Emergency Department / Diseño de un panel de indicadores para programas de optimización del uso de antimicrobianos en los Servicios de Urgencias

Objetivo: desarrollar un panel de indicadores para monitorizar la actividad de los programas de optimización del uso de antimicrobianos en los servicios de urgencias. Métodos: un grupo multidisciplinar formado por expertos en el manejo de la infección en urgencias y en la implantación de programas de optimización de uso de antimicrobianos (PROA) evaluó una propuesta de indicadores utilizando una metodología Delphi modificada. En una primera ronda, cada uno de los expertos clasificó la relevancia de cada indicador propuesto en 2 dimensiones (repercusión asistencial y facilidad de implantación) y 2 atributos (nivel de priorización y periodicidad de medida). La segunda ronda se realizó a partir del cuestionario modificado de acuerdo con las sugerencias planteadas y nuevos indicadores sugeridos por los participantes. Los expertos efectuaron modificaciones en el orden de priorización y calificaron los nuevos indicadores propuestos de la misma manera que en la primera ronda. Resultados: se propusieron un total de 61 potenciales indicadores divididos en 4 grupos: indicadores de consumo, microbiológicos, de proceso y de resultado. Tras el análisis de las puntuaciones y los comentarios realizados en la primera ronda, 31 indicadores fueron clasificados como de alta prioridad, 25 de prioridad intermedia y 5 de baja prioridad. Además se generaron 19 nuevos indicadores. Tras la segunda ronda, se mantuvieron los 61 indicadores inicialmente propuestos y adicionalmente se incorporaron 18 nuevos: 11 como de alta prioridad, 3 como de intermedia y 4 como de baja prioridad. Conclusiones: los expertos consensuaron un panel de indicadores PROA adaptado a los servicios de urgencias priorizados por nivel de relevancia como un elemento de ayuda para el desarrollo de estos programas, que contribuirá a monitorizar la adecuación del uso de antimicrobianos en estas unidades.(AU)

Objective: To develop a panel of indicators to monitor antimicrobial stewardship programs activity in the emergency department. Methods: A multidisciplinary group consisting of experts in the management of infection in emergency departments and the implementation of antimicrobial stewardship programs (ASP) evaluated a proposal of indicators using a modified Delphi methodology. In the first round, each expert classified the relevance of each proposed indicators in two dimensions (healthcare impact and ease of implementation) and two attributes (prioritization level and frequency). The second round was conducted based on the modified questionnaire according to the suggestions raised and new indicators suggested. Experts modified the prioritization order and rated the new indicators in the same manner as in the first round. Results: 61 potential indicators divided into four groups were proposed: consumption indicators, microbiological indicators, process indicators, and outcome indicators. After analyzing the scores and comments from the first round, 31 indicators were classified as high priority, 25 as intermediate priority, and 5 as low priority. Moreover, 18 new indicators were generated. Following the second round, all 61 initially proposed indicators were retained, and 18 new indicators were incorporated: 11 classified as high priority, 3 as intermediate priority, and 4 as low priority. Conclusions: The experts agreed on a panel of ASP indicators adapted to the emergency services prioritized by level of relevance. This is as a helpful tool for the development of these programs and will contribute to monitoring the appropriateness of the use of antimicrobials in these units.(AU)

Programas de optimización del uso de antimicrobianos en los servicios de urgencias españoles: Estudio PROA-URG / Antibiotic stewardship programs in the Spanish emergency services: PROA-URG Study

Introducción: Los programas de optimización de antimicrobianos (PROA) son herramientas clave en la adecuación de estos fármacos. La información disponible sobre la aplicación e indicadores para monitorizar estos programas en urgencias es limitada. El objetivo del estudio es conocer el grado de implantación de programas PROA en los servicios de urgencias, así como el uso de antimicrobianos en estas unidades. Material y métodos. Estudio multicéntrico retrospectivo. Se envió una invitación a todos los participantes del grupo de trabajo de farmacéuticos de urgencias REDFASTER-SEFH. Se utilizó un cuestionario de 21 ítems, contestado por un equipo formado por especialistas en los servicios de farmacia hospitalaria, urgencias, enfermedades infecciosas y microbiología. Resultados. 18 hospitales completaron la encuesta. Catorce (77,8%) disponían de un responsable PROA en la unidad. El valor de DDD por 1000 ingresos osciló entre 36,5 y 400,5 (mediana 100,4 [RIQ:57,2-157,3]). El grupo de carbapenémicos y macrólidos presentó una amplia variabilidad. Únicamente seis (33,3%) hospitales disponían de informe anual de resistencias específico para urocultivos y hemocultivos en urgencias. El porcentaje de multirresistentes en urocultivos fue del 12,5% y en hemocultivos del 12,2%. El porcentaje de adecuación en bacteremia de acuerdo con el resultado del hemocultivo fue del 81,0% (RIQ:74,6-85,0%), y en infección urinaria del 78,0% (RIQ:71,5-88,0%). Conclusiones. Pese a la existencia de responsables PROA, actividades formativas y guías de tratamiento en urgencias, la información sobre el uso de antimicrobianos y el perfil de resistencias en estas unidades es limitado. Futuras actividades han de ir encaminadas a mejorar la información sobre los resultados PROA propios para estas unidades. (AU)

Introduction: Antimicrobial stewardship programs (ASP) have become a key tool in the adaptation of these drugs to the health system. The information available on the application and indicators used in these programs in emergency departments is scarce. The objective of this study is to know theextent of ASP implementation in the emergency departments, as well as the use of antimicrobials in these units. Material and methods. Multicenter retrospective study. An invitation was sent to all participants of the REDFASTER-SEFH emergency pharmacist working group. A questionnaire was used consisting of 21 items, answered by a team made up of a pharmacist, emergency room specialist, infectious disease specialist and microbiologist. Results. Eighteen hospitals completed the survey. Fourteen (77.8%) had an ASP manager. The DDD value per 1000 admissions ranged between 36.5 and 400.5 (median: 100.4 [IQR:57.2-157.3]). Both carbapenem and macrolide group presented wide variability in use. Six (33.3%) hospitals had an annual report on the specific resistance profile for urine and blood cultures. The percentage of multi-drug resistant strains in urine cultures was 12.5% and in blood cultures 12.2%. The percentage of adequacy in the bacteremia treatment was 81.0% (IQR:74.6-85.0%), while in urinary tract infections was 78.0% (IQR:71.5-88.0). Conclusions: Despite the existence of ASP members in emergency services, as well as the training activity and local guidelines is common. knowledge of the use of antimicrobials and resistances is limited. Future activities must be aimed at improving information about the ASP results in these units. (AU)

On-Surface Synthesis of Non-Benzenoid Nanographenes Embedding Azulene and Stone-Wales Topologies.

The incorporation of non-benzenoid motifs in graphene nanostructures significantly impacts their properties, making them attractive for applications in carbon-based electronics. However, understanding how specific non-benzenoid structures influence their properties remains limited, and further investigations are needed to fully comprehend their implications. Here, we report an on-surface synthetic strategy toward fabricating non-benzenoid nanographenes containing different combinations of pentagonal and heptagonal rings. Their structure and electronic properties were investigated via scanning tunneling microscopy and spectroscopy, complemented by computational investigations. After thermal activation of the precursor P on the Au(111) surface, we detected two major nanographene products. Nanographene Aa-a embeds two azulene units formed through oxidative ring-closure of methyl substituents, while Aa-s contains one azulene unit and one Stone-Wales defect, formed by the combination of oxidative ring-closure and skeletal ring-rearrangement reactions. Aa-a exhibits an antiferromagnetic ground state with the highest magnetic exchange coupling reported up to date for a non-benzenoid containing nanographene, coexisting with side-products with closed shell configurations resulted from the combination of ring-closure and ring-rearragement reactions (Ba-a , Ba-s , Bs-a and Bs-s ). Our results provide insights into the single gold atom assisted synthesis of novel NGs containing non-benzenoid motifs and their tailored electronic/magnetic properties.

On-Surface Synthesis of a Radical 2D Supramolecular Organic Framework.

The design of supramolecular organic radical cages and frameworks is one of the main challenges in supramolecular chemistry. Their interesting material properties and wide applications make them very promising for (photo)redox catalysis, sensors, or host-guest spin-spin interactions. However, the high reactivity of radical organic systems makes the design of such supramolecular radical assemblies challenging. Here, we report the on-surface synthesis of a purely organic supramolecular radical framework on Au(111), by combining supramolecular and on-surface chemistry. We employ a tripodal precursor, functionalized with 7-azaindole groups that, catalyzed by a single gold atom on the surface, forms a radical molecular product constituted by a π-extended fluoradene-based radical core. The radical products self-assemble through hydrogen bonding, leading to extended 2D domains ordered in a Kagome-honeycomb lattice. This approach demonstrates the potential of on-surface synthesis for developing 2D supramolecular radical organic chemistry.

Design of a panel of indicators for antibiotic stewardship programs in the Emergency Department. / Diseño de un panel de indicadores para programas de optimización del uso de antimicrobianos en los Servicios de Urgencias.

OBJECTIVE: To develop a panel of indicators to monitor antimicrobial stewardship programs activity in the emergency department. METHODS: A multidisciplinary group consisting of experts in the management of infection in emergency departments and the implementation of antimicrobial stewardship programs (ASP) evaluated a proposal of indicators using a modified Delphi methodology. In the first round, each expert classified the relevance of each proposed indicators in two dimensions (healthcare impact and ease of implementation) and two attributes (prioritization level and frequency). The second round was conducted based on the modified questionnaire according to the suggestions raised and new indicators suggested. Experts modified the prioritization order and rated the new indicators in the same manner as in the first round. RESULTS: 61 potential indicators divided into four groups were proposed: consumption indicators, microbiological indicators, process indicators, and outcome indicators. After analyzing the scores and comments from the first round, 31 indicators were classified as high priority, 25 as intermediate priority, and 5 as low priority. Moreover, 18 new indicators were generated. Following the second round, all 61 initially proposed indicators were retained, and 18 new indicators were incorporated: 11 classified as high priority, 3 as intermediate priority, and 4 as low priority. CONCLUSIONS: The experts agreed on a panel of ASP indicators adapted to the emergency services prioritized by level of relevance. This is as a helpful tool for the development of these programs and will contribute to monitoring the appropriateness of the use of antimicrobials in these units.

Laparoscopic Sleeve Gastrectomy Lacks Intrasurgeon and Intersurgeon Agreement in Technical Key Points That May Affect Gastroesophageal Reflux Disease After the Procedure.

PURPOSE: Gastroesophageal reflux disease (GERD) after sleeve gastrectomy (SG) may be related to surgical technique. The fact that there is a lack of technical standardization may explain large differences in GERD incidence. The aim of this study is to evaluate auto- and hetero-agreement for SG technical key points based on recorded videos. METHODS: Ten experienced (minimum of 5 years performing bariatric surgery, minimum of 30 SG per year) bariatric surgeons (9 (90%) males) were selected. Participants were invited to send an unedited video with a typical laparoscopic SG (first round of the Delphi process). Videos were cropped into small clips comprising 11 key points of the technique. All anonymized clips (including their own) were returned to all surgeons. Individuals were asked to agree or not with the technique demonstrated (second round). The percentage of agreement was presented to the entire group that was asked for a second vote (third round). RESULTS: Agreement was poor/fair for all points except hiatal repair that had a very good agreement in the second round. For the third round, there was a slight increase in agreement for distance esophagogastric junction/proximal stapling and gastric mobilization for stapling and a slight decrease in agreement for gastric tube final shape. Only 1 (10%) surgeon recognized that he evaluated his own video. Five (50%) surgeons disagreed with themselves on 1 or more points. CONCLUSION: SG lacks intrasurgeon and intersurgeon agreement in technical key points that may justify significant differences in GERD incidence after the procedure.

[Translated article] Design of a panel of indicators for antibiotic stewardship programs in the Emergency Department.

OBJECTIVE: To develop a panel of indicators to monitor antimicrobial stewardship programs activity in the emergency department. METHODS: A multidisciplinary group consisting of experts in the management of infection in emergency departments and the implementation of antimicrobial stewardship programs (ASP) evaluated a proposal of indicators using a modified Delphi methodology. In the first round, each expert classified the relevance of each proposed indicators in two dimensions (healthcare impact and ease of implementation) and two attributes (prioritisation level and frequency). The second round was conducted based on the modified questionnaire according to the suggestions raised and new indicators suggested. Experts modified the prioritisation order and rated the new indicators in the same manner as in the first round. RESULTS: 61 potential indicators divided into four groups were proposed: consumption indicators, microbiological indicators, process indicators, and outcome indicators. After analysing the scores and comments from the first round, 31 indicators were classified as high priority, 25 as intermediate priority, and 5 as low priority. Moreover, 18 new indicators were generated. Following the second round, all 61 initially proposed indicators were retained, and 18 new indicators were incorporated: 11 classified as high priority, 3 as intermediate priority, and 4 as low priority. CONCLUSIONS: The experts agreed on a panel of ASP Indicators adapted to the emergency services prioritised by level of relevance. This is as a helpful tool for the development of these programs and will contribute to monitoring the appropriateness of the use of antimicrobials in these units.

Epitaxial growth and characterization of SnSe phases on Au(111).

Two-dimensional (2D) layered group IV-VI semiconductors attract great interest due to their potential applications in nanoelectronics. Depending on the dimensionality, different phases of the same material can present completely different electronic and optical properties, expanding its applications. Here, we present a combined experimental and theoretical study of the atomic structure and electronic properties of epitaxial SnSe structures grown on a metallic Au(111) substrate, forming almost defect-free 2D layers. We describe a coverage-dependent transition from a metallicß-SnSe to a semiconductingα-SnSe phase. The combination of scanning tunneling microscopy/spectroscopy, non-contact atomic force microscopy, x-ray photoelectron spectroscopy/diffraction and angle-resolved photoemission spectroscopy, complemented by density functional theory, provides a comprehensive study of the geometric and electronic structure of both phases. Our work demonstrates the possibility to grow two distinct SnSe phases on Au(111) with high quality and on a large scale. The strong interaction with the substrate allows the stabilization of the previously experimentally unreportedß-SnSe, while the ultra-thin films of orthorhombicα-SnSe are structurally and electronically equivalent to bulk SnSe.

Inflammatory processes involved in the alteration of liver function biomarkers in adult hospitalized patients treated with parenteral nutrition.

Introduction: Liver damage has been associated with the accumulation of phytosterols (PS) in patients treated with parenteral nutrition (PN). We aimed to study the association of inflammatory markers with liver function biomarker (LFB) alterations in patients treated with PN containing PS. Materials and methods: Prospective observational study. Simple linear and stepwise multiple linear regression tests and interactions were performed. Results: Nineteen patients were included. In the multivariable model, determinations based on LFBs as dependent and phytosterols (and their fractions) as independent variables showed an association between increases in gamma-glutamyltransferase (GGT) and lanosterol (p < 0.001), stigmasterol (p < 0.001), interleukin-10 (IL-10) × total phytosterols (Phyt) (p < 0.009), tumor necrosis factor-α (TNF-α) × Phyt (p < 0.002), IL-10 × sitosterol (p < 0.002), TNF-α × sitosterol (p < 0.001), IL-10 × campesterol (p < 0.033), IL-10 (p < 0.006 and p < 0.015), TNF-α (p < 0.048 and p < 0.027). Increases in alanine aminotransferase (ALT) were associated with Phyt (p < 0.006), lanosterol (p < 0.016), C-reactive protein (CRP) × campesterol (p < 0.001), interleukin-6 (IL-6) × stigmasterol (p < 0.030), CRP (p < 0.08), and IL-6 (p < 0.042). Alkaline phosphatase (AP) increases were associated with CRP (p < 0.002). Discussion: Inflammation in the presence of plasmatic PS seems to have a synergistic effect in impairing liver function, mainly altering GGT but also ALT.

Steering Large Magnetic Exchange Coupling in Nanographenes near the Closed-Shell to Open-Shell Transition.

The design of open-shell carbon-based nanomaterials is at the vanguard of materials science, steered by their beneficial magnetic properties like weaker spin-orbit coupling than that of transition metal atoms and larger spin delocalization, which are of potential relevance for future spintronics and quantum technologies. A key parameter in magnetic materials is the magnetic exchange coupling (MEC) between unpaired spins, which should be large enough to allow device operation at practical temperatures. In this work, we theoretically and experimentally explore three distinct families of nanographenes (NGs) (A, B, and C) featuring majority zigzag peripheries. Through many-body calculations, we identify a transition from a closed-shell ground state to an open-shell ground state upon an increase of the molecular size. Our predictions indicate that the largest MEC for open-shell NGs occurs in proximity to the transition between closed-shell and open-shell states. Such predictions are corroborated by the on-surface syntheses and structural, electronic, and magnetic characterizations of three NGs (A[3,5], B[4,5], and C[4,3]), which are the smallest open-shell systems in their respective chemical families and are thus located the closest to the transition boundary. Notably, two of the NGs (B[4,5] and C[4,3]) feature record values of MEC (close to 200 meV) measured on the Au(111) surface. Our strategy for maximizing the MEC provides perspectives for designing carbon nanomaterials with robust magnetic ground states.

Design and Manipulation of a Minimalistic Hydrocarbon Nanocar on Au(111).

Nanocars are carbon-based single-molecules with a precise design that facilitates their atomic-scale control on a surface. The rational design of these molecules is important in atomic and molecular-scale manipulation to advance the development of molecular machines, as well as for a better understanding of self-assembly, diffusion and desorption processes. Here, we introduce the molecular design and construction of a collection of minimalistic nanocars. They feature an anthracene chassis and four benzene derivatives as wheels. After sublimation and adsorption on an Au(111) surface, we show controlled and fast manipulation of the nanocars along the surface using the tip of a scanning tunneling microscope (STM). The mechanism behind the successful displacement is the induced dipole created over the nanocar by the STM tip. We utilized carbon monoxide functionalized tips both to avoid decomposition and accidentally picking the nanocars up during the manipulation. This strategy allowed thousands of maneuvers to successfully win the Nanocar Race II championship.

Effect of Fish Oil Parenteral Emulsion Supplementation on Inflammatory Parameters after Esophagectomy.

(Background) Esophagectomy (EPG) presents high morbidity and mortality. Omega-3 fatty acids (ω-3FA) are a pharmaconutrient with benefits for postoperative morbidity. Studies of ω-3FA administered parenterally after esophagectomy are scarce. This study proposes to investigate the effect of combining fish oil lipid emulsions (LE) administered parenterally with enteral nutrition support. (Methods) Randomization was 1:1:1 in three groups: Group A received a LE mixture of 0.4 g/kg/day of fish oil and 0.4 g/kg/day of LCT/MCT 50:50, Group B received 0.8 g/kg/day of fish oil LE, and Group C received 0.8 g/kg/day of LCT/MCT 50:50. Variables were measured at recruitment time and day +1, +3, and +5. Inflammatory variables studied were Interlukin-6, C-reactive protein (CRP), tumoral necrosis factor-α (TNF-α), IL-10, IL-8 and CD25s. Safety, nutritional parameters and complications were analyzed. (Results) Administration of ω-3LE in the immediate postoperative period did not modulate the earlier inflammatory response. Statistically significant differences were found in IL-6 and CRP overall temporal evolution but were not found when studying the type of LE administered or in patients needing critical care. Administration of ω-3 resulted in safe and improved hypertriglyceridemia, depending on the dose. (Conclusions) ω-3FA has no impact on the early inflammatory postoperative response assessed for a short period but was safe. More studies for longer periods are needed.

COVID-19 dynamics in Madrid (Spain): A new convolutional model to find out the missing information during the first three waves.

This article presents a novel mathematical model to describe the spread of an infectious disease in the presence of social and health events: it uses 15 compartments, 7 convolution integrals and 4 types of infected individuals, asymptomatic, mild, moderate and severe. A unique feature of this work is that the convolutions and the compartments have been selected to maximize the number of independent input parameters, leading to a 56-parameter model where only one had to evolve over time. The results show that 1) the proposed mathematical model is flexible and robust enough to describe the complex dynamic of the pandemic during the first three waves of the COVID-19 spread in the region of Madrid (Spain) and 2) the proposed model allows us to calculate the number of asymptomatic individuals and the number of persons who presented antibodies during the first waves. The study shows that the following results are compatible with the reported data: close to 28% of the infected individuals were asymptomatic during the three waves, close to 29% of asymptomatic individuals were detected during the subsequent waves and close to 26% of the Madrid population had antibodies at the end of the third wave. This calculated number of persons with antibodies is in great agreement with four direct measurements obtained from an independent sero-epidemiological research. In addition, six calculated curves (total number of confirmed cases, asymptomatic who are confirmed as positive, hospital admissions and discharges and intensive care units admissions) show good agreement with data from an epidemiological surveillance database.

Interplay between π-Conjugation and Exchange Magnetism in One-Dimensional Porphyrinoid Polymers.

The synthesis of novel polymeric materials with porphyrinoid compounds as key components of the repeating units attracts widespread interest from several scientific fields in view of their extraordinary variety of functional properties with potential applications in a wide range of highly significant technologies. The vast majority of such polymers present a closed-shell ground state, and, only recently, as the result of improved synthetic strategies, the engineering of open-shell porphyrinoid polymers with spin delocalization along the conjugation length has been achieved. Here, we present a combined strategy toward the fabrication of one-dimensional porphyrinoid-based polymers homocoupled via surface-catalyzed [3 + 3] cycloaromatization of isopropyl substituents on Au(111). Scanning tunneling microscopy and noncontact atomic force microscopy describe the thermal-activated intra- and intermolecular oxidative ring closure reactions as well as the controlled tip-induced hydrogen dissociation from the porphyrinoid units. In addition, scanning tunneling spectroscopy measurements, complemented by computational investigations, reveal the open-shell character, that is, the antiferromagnetic singlet ground state (S = 0) of the formed polymers, characterized by singlet-triplet inelastic excitations observed between spins of adjacent porphyrinoid units. Our approach sheds light on the crucial relevance of the π-conjugation in the correlations between spins, while expanding the on-surface synthesis toolbox and opening avenues toward the synthesis of innovative functional nanomaterials with prospects in carbon-based spintronics.

Resolving Atomic-Scale Defects in Conjugated Polymers On-Surfaces.

Atomic scale defects significantly affect the mechanical, electronic, and optical properties of π-conjugated polymers. Here, isolated atomic-scale defects are deliberately introduced into a prototypical anthracene-ethynylene π-conjugated polymer, and its local density of states is carefully examined on the atomic scale to show how individual defects modify the inherent electronic and magnetic properties of this one-dimensional systems. Scanning tunneling and atomic force microscopy experiments, supplemented with density functional theory calculations, reveal the existence of a sharp electronic resonance at the Fermi energy around certain defects, which is associated with the formation of a local magnetic moment accompanied by substantial mitigation of the mobility of charge carriers. While defects in traditionally synthesized polymers lead to arbitrary conformations, the presented results clearly reflect the preferential formation of low dimensional defects at specific polymer sites, which may introduce the possibility of engineering macroscopic defects in surface-synthesized conjugated polymers.

Surface-Assisted Synthesis of N-Containing π-Conjugated Polymers.

On-surface synthesis has recently emerged as a powerful strategy to design conjugated polymers previously precluded in conventional solution chemistry. Here, an N-containing pentacene-based precursor (tetraazapentacene) is ex-professo synthesized endowed with terminal dibromomethylene (:CBr2 ) groups to steer homocoupling via dehalogenation on metallic supports. Combined scanning probe microscopy investigations complemented by theoretical calculations reveal how the substrate selection drives different reaction mechanisms. On Ag(111) the dissociation of bromine atoms at room temperature triggers the homocoupling of tetraazapentacene units together with the binding of silver adatoms to the nitrogen atoms of the monomers giving rise to a N-containing conjugated coordination polymer (P1). Subsequently, P1 undergoes ladderization at 200 °C, affording a pyrrolopyrrole-bridged conjugated polymer (P2). On Au(111) the formation of the intermediate polymer P1 is not observed and, instead, after annealing at 100 °C, the conjugated ladder polymer P2 is obtained, revealing the crucial role of metal adatoms on Ag(111) as compared to Au(111). Finally, on Ag(100) the loss of :CBr2 groups affords the formation of tetraazapentacene monomers, which coexist with polymer P1. Our results contribute to introduce protocols for the synthesis of N-containing conjugated polymers, illustrating the selective role of the metallic support in the underlying reaction mechanisms.

Psychosocial factors in adherence to pharmacological treatment and diabetes mellitus control in patients over 65 / Factores psicosociales en la adherencia al tratamiento farmacológico y el control de la diabetes mellitus en pacientes mayores de 65 años

Aim: To explore the influence of anxiety/depression symptoms and social risk in patients older than 65 years with type 2 diabetes mellitus (T2DM) both in non-adherence to pharmacological treatment (Non-AdhT) and in poor control of T2DM. Design: Cross-sectional study.Setting and participantsAdults over 65 years of age with T2DM treated at the Madrid Primary Care Service. Main measurements: Data collection: Electronic Health Record database. Variables: Poor control of T2DM (HBA1c) and Non-AdhT (Morisky-Green test); main clinical variables: symptoms of depression/anxiety and social risk. Global multivariate logistic regression models and disaggregated by sex were used to Non-AdhT and poor T2DM control. Results: Data were obtained on 884 subjects. Non-AdhT prevalence: 4.4%; prevalence of poor T2DM control: 37.2%. Multivariate logistic regression models for No-AdhT in men showed a higher risk if they had symptoms of anxiety/depression (OR: 3.88; 95%CI: 1.15–13.07); and in women, if they had social risk (OR: 5.61; 95%CI: 1.86–16.94). Multivariate logistic regression models for poor control of T2DM in men revealed a higher risk if they did not have AdhT (OR: 3.53; 95%CI: 1.04–12.02). Conclusions: In people over 65 years with T2DM, although Non-AdhT is low, the prevalence of poor T2DM control is high. Symptoms of depression or anxiety are a risk factor to Non-AdhT in men, while social risk has the same effect in women. Non-AdhT in men increases the risk of poor T2DM control. From a gender perspective, it is important to detect social and mental health problems in older adults with diabetes and to reinforce strategies to improve their adherence to drug treatment in these patients.(AU)

Objetivo: Explorar la influencia de los síntomas de ansiedad/depresión y del riesgo social en pacientes mayores de 65 años con diabetes mellitus tipo 2 (DM2), tanto en la no adherencia al tratamiento farmacológico (no AdhT) como en el mal control de la DM2.Diseño: Estudio descriptivo transversal. Emplazamiento y participantesAdultos mayores de 65 años con DM2 atendidos en el Servicio de Atención Primaria de Madrid.Principales mediciones: Recogida de datos: base de datos de historia clínica electrónica. Variables: mal control de T2DM (HBA1c) y no AdhT (prueba de Morisky-Green); principales variables clínicas: síntomas de depresión/ansiedad y riesgo social. Se utilizaron modelos globales de regresión logística multivariante y desagregados por sexo para no AdhT y mal control de DM2. Resultados: Se obtuvieron datos de 884 sujetos. Prevalencia de no AdhT: 4,4%; prevalencia de mal control de DM2: 37,2%. Los modelos de regresión logística multivariante para no AdhT en hombres mostraron un mayor riesgo si tenían síntomas de ansiedad/depresión (OR: 3,88; IC del 95%: 1,15-13,07); y en mujeres, si tenían riesgo social (OR: 5,61; IC del 95%: 1,86-16,94). Los modelos de regresión logística multivariante para el control deficiente de la DM2 en los hombres revelaron un mayor riesgo si no tenían AdhT (OR: 3,53; IC del 95%: 1,04-12,02). Conclusiones: En personas mayores de 65 años con DM2, aunque la no AdhT es baja, la prevalencia de mal control de la DM2 es alta. Los síntomas de depresión o ansiedad son un factor de riesgo de no AdhT en los hombres, mientras que el riesgo social tiene el mismo efecto en las mujeres. La no AdhT en los hombres aumenta el riesgo de un control deficiente de la DM2. Desde una perspectiva de género, es importante detectar problemas de salud social y mental en adultos mayores con diabetes y reforzar estrategias para mejorar su adherencia al tratamiento farmacológico y control glucémico en estos pacientes.(AU)