Remembering the Old Propensity Rules of the Electromagnetic Enhancement Mechanism of SERS: Reorientation of Pyridine on a Silver Electrode Induced by the Applied Potential.

Electrochemical SERS of pyridine adsorbed on a silver electrode has been analyzed by comparing the spectra to the calculated normal Raman and resonance Raman intensities of model systems of pyridine bonded to linear silver clusters with different densities of charge through the nitrogen (Ag-NPy) or flipped through the hydrogen in the para-position (Ag-HPy). The changes observed in the ν(CH) region of the SERS have been investigated for the first time and related to a molecular reorientation at negative surface excess of charge of the metal in such a way that the ν(CH) bands with the highest (mode 2) and lowest (mode 13) wavenumber dominate this spectral region at positive or negative electrode potentials, respectively. The calculations support that the ν(CH) region is dominated by a specific vibration depending on pyridine orientation and suggest that both species coexist in the SERS recorded at negative potentials. This conclusion is supported by the SERS of centrosymmetric pyrazine which do not show this behavior and remembers the predictions from the old propensity rules of the so-called electromagnetic mechanism of SERS.

Conformal TiO2 Aerogel-Like Films by Plasma Deposition: from Omniphobic Antireflective Coatings to Perovskite Solar Cell Photoelectrodes.

The ability to control the porosity of thin oxide films is a key factor determining their properties. Despite the abundance of dry processes for synthesizing oxide porous layers, a high porosity range is typically achieved by spin-coating-based wet chemical methods. Besides, special techniques such as supercritical drying are required to replace the pore liquid with air while maintaining the porous network. In this study, we propose a new method for the fabrication of ultraporous titanium dioxide thin films at room or mild temperatures (T ≤ 120 °C) by a sequential process involving plasma deposition and etching. These films are conformal to the substrate topography even for high-aspect-ratio substrates and show percolated porosity values above 85% that are comparable to those of advanced aerogels. The films deposited at room temperature are amorphous. However, they become partly crystalline at slightly higher temperatures, presenting a distribution of anatase clusters embedded in the sponge-like open porous structure. Surprisingly, the porous structure remains after annealing the films at 450 °C in air, which increases the fraction of embedded anatase nanocrystals. The films are antireflective, omniphobic, and photoactive, becoming superhydrophilic when subjected to ultraviolet light irradiation. The supported, percolated, and nanoporous structure can be used as an electron-conducting electrode in perovskite solar cells. The properties of the cells depend on the aerogel-like film thickness, which reaches efficiencies close to those of commercial mesoporous anatase electrodes. This generic solvent-free synthesis is scalable and applicable to ultrahigh porous conformal oxides of different compositions, with potential applications in photonics, optoelectronics, energy storage, and controlled wetting.

Unusually severe neonatal presentation of mediastinal bronchogenic cyst.

Bronchogenic cysts are rare congenital malformations that occur in adults and children, with differences in distribution and presentation. We present the case of a newborn who initiated respiratory distress from the first minutes of life, presenting with hypoventilation and rightward displacement of the cardiac impulse, requiring oxygen therapy and intubation. The first radiograph shows a left pulmonary emphysema. The computerized axial tomography revealed a large mediastinal mass causing an obstructive syndrome of the left bronchus. The mass was successfully excised, resulting in a favorable clinical evolution. Although the presentation of our case is exceptional, it is worth noting that while most bronchogenic cysts are asymptomatic, they can occur in childhood, even from birth, as in our case.

Prevalence of childhood obesity in Spain and its relation with socioeconomic status and health behaviors: Population-based cross-sectional study.

OBJECTIVES: This study aims to assess the current state of childhood overweight and obesity in Spain, and its relationship with socioeconomic status and health-related behaviors. METHODS: Population-based cross-sectional observational study, based on the 2017 National Health Survey in minors in Spain. This study included all children surveyed who were aged 1-14 years. Childhood obesity was estimated from the z-score of the body mass index. RESULTS: The study included 4882 children aged 1-14 years (mean 7.5). The prevalence of obesity was 18.6% (95% confidence interval [CI] 18.5-18.7), while 13.5% (95% CI 13.4-13.6) were overweight. These figures represent over a million children in Spain who are obese and nearly 750,000 who are overweight. A north-south geographic gradient was apparent, with higher prevalence of unhealthy body weight in southern Spain. Factors associated with childhood obesity were low socioeconomic status, poor diet and sedentarism, among others. CONCLUSIONS: Childhood overweight in Spain is strongly associated with socioeconomic status and other factors such as diet and sedentarism. Multidisciplinary public health interventions are needed to reduce this serious health problem in children.

Linear Vibronic Coupling Approach for Surface-Enhanced Raman Scattering: Quantifying the Charge-Transfer Enhancement Mechanism.

The outstanding amplification observed in surface-enhanced Raman scattering (SERS) is due to several enhancement mechanisms, and standing out among them are the plasmonic (PL) and charge-transfer (CT) mechanisms. The theoretical estimation of the enhancement factors of the CT mechanism is challenging because the excited-state coupling between bright plasmons and dark CT states must be properly introduced into the model to obtain reliable intensities. In this work, we aim at simulating electrochemical SERS spectra, considering models of pyridine on silver clusters subjected to an external electric field E⃗ that represents the effect of an electrode potential Vel. The method adopts quantum dynamical propagations of nuclear wavepackets on the coupled PL and CT states described with linear vibronic coupling models parametrized for each E⃗ through a fragment-based maximum-overlap diabatization. By presenting results at different values of E⃗, we show that indeed there is a relation between the population transferred to the CT states and the total scattered intensity. The tuning and detuning processes of the CT states with the bright PLs as a function of the electric field are in good agreement with those observed in experiments. Finally, our estimations for the CT enhancement factors predict values in the order of 105 to 106, meaning that when the CT and PL states are both in resonance with the excitation wavelength, the CT and PL enhancements are comparable, and vibrational bands whose intensity is amplified by different mechanisms can be observed together, in agreement with what was measured by typical experiments on silver electrodes.

Risk factors for major adverse cardiovascular events in postmenopausal women: UK Biobank prospective cohort study.

BACKGROUND AND AIMS: Cardiovascular risk increases during menopause, so the medical and scientific community should consider women's specific risk factors to prevent cardiovascular disease. This study aims to assess the risk factors for the incidence of major adverse cardiovascular events (MACE) exclusive to postmenopausal women. METHODS: We conducted a prospective cohort study in postmenopausal women aged 40 years and older, who were included in the UK Biobank cohort between 2006 and 2010 and followed to 2021 (12 years). A total of 156,787 women were followed for a median of 12.5 years (nearly 2 million person-years), and MACE risk was assessed using Fine-Gray competing risk models. RESULTS: The cumulative incidence of cardiovascular morbidity and mortality was 1.2% (0.97 cases per 1000 women-years). Not having taken birth control pills, not having children, and early menarche (≤12 years) were independently associated with cardiovascular morbidity and mortality. CONCLUSIONS: Risk factors for cardiovascular disease that are specific to women include early menarche, not having taken oral contraceptives, and reproductive history, and this relationship is independent of classic cardiovascular risk factors.

Risk factors for low humoral response to BNT-162b2 in hemodialysis patients.

INTRODUCTION: Maintenance hemodialysis (HD) patients are at higher risk of both infection and mortality associated with the new SARS-CoV-2. Immunization through large-scale vaccination is the cornerstone of infection prevention in this population. This study aims to identify risk factors for low response to the BNT-162b2 (Pfizer BioNTech) vaccine in an HD cohort. MATERIALS AND METHODS: Observational prospective study of an HD group followed in a Portuguese Public Founded Hemodialysis Center who received BNT-162b2 vaccination. Specific anti-Spike IgG was evaluated as arbitrary units per milliliter (AU/mL) and compared against risk factors. RESULTS: Humoral response evaluated by IgG anti-Spike levels showed a strong correlation with Charlson comorbidity index (CCI) and intact parathormone (iPTH) after each inoculation (1st dose: rho = -0.64/0.54; 2nd dose: rho = -0.66/0.63, respectively; p < 0.01 throughout). After completing both doses: 1) no response (NR) was associated with female sex (p < 0.01), lower albumin and iPTH (p = 0.01); 2) weak response (WR) showed higher CCI, older age, lower iPTH, and lower albumin (p = < 0.01, p = 0.03, p < 0.01, p = 0.05, respectively). A binary regression model using CCI, sex (male), and central venous catheter (CVC) was statistically significant in prediction of WR after the 2nd dose with OR (95% CI): 1.81 (1.06 - 3.08); 0.05 (0.01 - 0.65); 13.55 (1.06 - 174.18), respectively (p = 0.01). CONCLUSION: Older age, higher CCI, lower iPTH and albumin as well as CVC as vascular access were associated with lower response to vaccination in our study. Comorbidity burden is suggested as a preferred indirect method to predict worst response when compared to age alone.

Conservative treatment of ameloblastoma: report of 2 cases and review of the literature / Tratamiento conservador de ameloblastoma: reporte de 2 casos y revisión de la literatura

Introduction: ameloblastomas correspond to one of the most prevalent odontogenic tumors in developing countries, they are mainly located in the mandible, and their treatment has been widely discussed over the years, using radical or conservative treatments depending on different variables. Clinical case: we present two cases of patients with ameloblastoma who underwent conservative treatment without the use of adjuvant therapy, obtaining satisfactory results at 36 and 48 months. Discussion: due to a possible recurrence with conservative treatment, radical management has been suggested, however, the choice of treatment should be based on a series of clinical, histological, and radiographic characteristics.

Introducción: Los ameloblastomas corresponden a uno de los tumores odontogénicos más prevalentes en los países en desarrollo, se ubican principalmente en la mandíbula, y su tratamiento ha sido ampliamente discutido a lo largo de los años, utilizando tratamientos radicales o conservadores dependiendo de distintas variables. Caso clínico: se presentan dos casos de pacientes con un ameloblastoma a quienes se les realizó tratamiento conservador sin uso de terapia coadyuvante, obteniendo resultados satisfactorios a los 36 y 48 meses. Discusión: Debido a una posible recurrencia con un tratamiento conservador, se ha sugerido manejo radical, sin embargo, la elección de tratamiento debe ser en base a una serie de características clínicas, histológicas y radiográficas.

Eculizumab discontinuation in a patient with atypical hemolytic uremic syndrome after ChAdOx1 nCoV-19 vaccination.

Eculizumab has proven to be effective in patients with atypical hemolytic uremic syndrome (aHUS) in clinical trials and in the real world, but the optimal duration of therapy remains unknown. Standard maintenance treatment is often life-long, but the possibility of discontinuation has not yet been systematically tested. We describe a case of aHUS after ChAdOx1 nCoV-19 vaccination in a patient with homozygous CFHR3/CFHR1 gene deletion who discontinued eculizumab maintenance therapy 24 weeks after achieving disease remission. We report the safety of discontinuing eculizumab treatment with the aim of minimizing the risk of adverse reactions, reducing the risk of meningitis, improving quality of life, and reducing the considerable treatment costs.

Higher daily temperature range at depth is linked with higher thermotolerance in antipatharians from the canary islands.

Sensitivity to ocean warming is generally expected to be lower in populations from more heterogeneous thermal environments, owing to greater phenotypic plasticity and/or genotype selection. While resilience of benthic populations from thermally fluctuating environments has been investigated at a variety of spatial scales, this has received limited attention across depths and has remained unresolved for Antipatharian corals, key habitat-forming species across a wide bathymetric range in all of the world oceans. In this study, we aimed at addressing the thermal sensitivity of Antipatharian corals across depths characterized by different levels of temperature fluctuations. We used an acute ramping experimental approach to compare the thermal sensitivity of colonies of (1) the branched Antipatharian Antipathella wollastoni (Gray, 1857) from two distinct depths (25 and 40 m) in Gran Canaria (Canary Islands, Spain); and of (2) unbranched mesophotic (80 m) Stichopathes species, from Lanzarote (Canary Islands, Spain; S. gracilis (Gray, 1857)), and Stichopathes sp. clade C from Mo'orea, French Polynesia. Results showed that the daily temperature range in Gran Canaria was larger at mesophotic depths (3.9 °C vs. 2.8 °C at 40 and 25 m, respectively) and this coincided with lower thermal sensitivity in mesophotic colonies of A. wollastoni. Second, S. gracilis from Lanzarote showed a lower thermal sensitivity than the previously studied Stichopathes sp. clade C from Mo'orea (French Polynesia) inhabiting a less variable habitat. These results are in line with the climate variability hypothesis, which states that populations under more variable thermal conditions have a lower sensitivity to warming than those from more stable environments, as they have adapted/acclimated to these higher levels of temperature fluctuations.

Levelling-up rhodolith-bed science to address global-scale conservation challenges.

Global marine conservation remains fractured by an imbalance in research efforts and policy actions, limiting progression towards sustainability. Rhodolith beds represent a prime example, as they have ecological importance on a global scale, provide a wealth of ecosystem functions and services, including biodiversity provision and potential climate change mitigation, but remain disproportionately understudied, compared to other coastal ecosystems (tropical coral reefs, kelp forests, mangroves, seagrasses). Although rhodolith beds have gained some recognition, as important and sensitive habitats at national/regional levels during the last decade, there is still a notable lack of information and, consequently, specific conservation efforts. We argue that the lack of information about these habitats, and the significant ecosystem services they provide, is hindering the development of effective conservation measures and limiting wider marine conservation success. This is becoming a pressing issue, considering the multiple severe pressures and threats these habitats are exposed to (e.g., pollution, fishing activities, climate change), which may lead to an erosion of their ecological function and ecosystem services. By synthesizing the current knowledge, we provide arguments to highlight the importance and urgency of levelling-up research efforts focused on rhodolith beds, combating rhodolith bed degradation and avoiding the loss of associated biodiversity, thus ensuring the sustainability of future conservation programs.

Better Anti-Spike IgG Antibody Response to SARS-CoV-2 Vaccine in Patients on Haemodiafiltration than on Haemodialysis.

INTRODUCTION: The antibody response to SARS-CoV-2 vaccine in haemodialysis (HD) patients is diminished compared to healthy subjects. The aim of this study was to compare the presence of reactive SARS-CoV-2 antibodies in patients with high-flux HD and on-line haemodiafiltration (HDF) three and 6 months after the second dose of SARS-CoV-2 vaccine since previous studies indicate that a sustained antibody response correlates with protection from disease. METHODS: We included 216 HD patients of which 157 had on-line HDF and 59 high-flux HD and 46 health care workers as controls and studied the presence of reactive anti-spike IgG antibodies three and 6 months after the second dose of SARS-CoV-2 vaccine. Clinical features between the patient groups were similar, but patients with on-line HDF had significantly higher Kt/V. RESULTS: The percentage of participants with reactive antibodies was significantly lower in patients compared to controls, both three and 6 months after the second dose of vaccine. Furthermore, the proportion of patients with reactive anti-spike IgG ≥1.0 6 months after the second dose of vaccine was significantly higher in patients with on-line HDF compared to in patients with high-flux HD. In logistic regression analyses adjusted for several clinical features, the variables associated with presence of reactive anti-spike IgG at 3 months after the second dose of vaccine were lower age, HDF treatment, not being obese and not having a previous solid organ transplant. The two variables with the strongest influence on the presence of reactive anti-spike IgG levels 6 months after the second dose of vaccine were treatment with on-line HDF and not having immunosuppressive therapy. CONCLUSION: This is the first study to show that on-line HDF preserves the antibody response better than high-flux HD after vaccination with SARS-CoV-2 vaccine. Treatment strategies that sustain the vaccine response are essential to apply in this vulnerable group of patients.

Black coral forests enhance taxonomic and functional distinctiveness of mesophotic fishes in an oceanic island: implications for biodiversity conservation.

The degradation of shallow ecosystems has called for efforts to understand the biodiversity and functioning of Mesophotic Ecosystems. However, most empirical studies have been restricted to tropical regions and have majorly focused on taxonomic entities (i.e., species), neglecting important dimensions of biodiversity that influence community assembly and ecosystem functioning. Here, using a subtropical oceanic island in the eastern Atlantic Ocean (Lanzarote, Canary Islands), we investigated variation in (a) alpha and (b) beta functional (i.e., trait) diversity across a depth gradient (0-70 m), as a function of the presence of black coral forests (BCFs, order Antipatharian) in the mesophotic strata, a vulnerable but often overlooked 'ecosystem engineer' in regional biodiversity. Despite occupying a similar volume of the functional space (i.e., functional richness) than shallow (< 30 m) reefs, mesophotic fish assemblages inhabiting BCFs differed in their functional structure when accounting for species abundances, with lower evenness and divergence. Similarly, although mesophotic BCFs shared, on average, 90% of the functional entities with shallow reefs, the identity of common and dominant taxonomic and functional entities shifted. Our results suggest BCFs promoted the specialization of reef fishes, likely linked to convergence towards optimal traits to maximize the use of resources and space. Regional biodiversity planning should thus focus on developing specific management and conservation strategies for preserving the unique biodiversity and functionality of mesophotic BCFs.

Mapping and assessing seagrass meadows changes and blue carbon under past, current, and future scenarios.

Seagrasses store large amounts of blue carbon and mitigate climate change, but they have suffered strong regressions worldwide in recent decades. Blue carbon assessments may support their conservation. However, existing blue carbon maps are still scarce and focused on certain seagrass species, such as the iconic genus Posidonia, and intertidal and very shallow seagrasses (<10 m depth), while deep-water and opportunistic seagrasses have remained understudied. This study filled this gap by mapping and assessing blue carbon storage and sequestration by the seagrass Cymodocea nodosa in the Canarian archipelago using the local carbon storage capacity and high spatial resolution (20 m/pixel) seagrass distribution maps for the years 2000 and 2018. Particularly, we mapped and assessed the past, current and future capacity of C. nodosa to store blue carbon, according to four plausible future scenarios, and valued the economic implications of these scenarios. Our results showed that C. nodosa has suffered ca. 50 % area loss in the last two decades, and, if the current degradation rate continues, our estimations demonstrate that it could completely disappear in 2036 ("Collapse scenario"). The impact of these losses in 2050 would reach 1.43 MT of CO2 equivalent emitted with a cost of 126.3 million € (0.32 % of the current Canary GDP). If, however, this degradation is slow down, between 0.11 and 0.57 MT of CO2 equivalent would be emitted until 2050 ("Intermediate" and "Business-as-usual" scenarios, respectively), which corresponds to a social cost of 3.63 and 44.81 million €, respectively. If the current seagrass extension is maintained ("No Net Loss"), 0.75 MT of CO2 equivalent would be sequestered from now to 2050, which corresponds to a social cost saving of 73.59 million €. The reproducibility of our methodology across coastal ecosystems underpinned by marine vegetation provides a key tool for decision-making and conservation of these habitats.

Peritoneal Dialysis Exit-Site Care Protocols in Portugal and Its Association with Catheter-Related Infections.

INTRODUCTION: Exit-site infection (ESi) prevention is a key factor in lowering the risk of peritonitis. This study aimed to evaluate the associations between exit-site (ES) care protocols and the annual incidence rates of ESi and peritonitis in Portugal. METHODS: We performed a national survey using two questionnaires: one about the incidence of catheter-related infections and the other characterizing patients' education and ES care protocols. RESULTS: In 2017 and 2018, 14 Portuguese units followed 764 and 689 patients. ESi incidence rate was 0.41 episodes/year, and the peritonitis incidence rate was 0.37. All units monitor catheter-related infections on a yearly basis, use antibiotic prophylaxis at the time of catheter placement, and treat nasal carriage of S. aureus, although with different approaches. Screening for nasal carriage of S. aureus is performed by 12 units, and daily topical antibiotic cream is recommended by 6 out of 14 of the units. We did not find statistical differences in ESi/peritonitis, comparing these practices. The rate of ESis was lower with nonocclusive dressing immediately after catheter insertion, bathing without ES dressing, with the use of colostomy bags in beach baths and was higher with the use of bath sponge. The peritonitis rate was lower with bathing without ES dressing and if shaving of the external cuff was performed in the presence of chronic ESi. CONCLUSIONS: We found potential proceedings associated with ESi and peritonitis. A regular national audit of peritoneal dialysis units is an important tool for clarifying the best procedures for reduction of catheter-related infections.

Emotional impact on children during home confinement in Spain.

Introduction: The COVID-19 pandemic has brought about important changes. On March 14, 2020, a strict home confinement was decreed in Spain. Children did not attend school and were not allowed to leave their homes. The aim of this study was to determine the emotional state of these children, as well as associated factors. Material and methods: A cross-sectional descriptive study was conducted using an online questionnaire sent by cell phone. This survey includes sociodemographic items and questions concerning the emotional impact of the lockdown. With the questions on emotions, two categories of emotional state were established with the variables fear, irritability, sadness and somatization: those who were less or more emotionally affected. A multivariate logistic model was used to estimate the associations between the variables. Results: A total of 3,890 responses were obtained. The mean age of the children was 6.78 years (range 0 to 16). A score indicating poor emotional state was reported by 40.12%. The multivariate logistic model for poor emotional state was directly associated with having less appetite, sleep disturbances, and with parents' beliefs that their child will have difficulties returning to normal life after lockdown. A better emotional state was associated with being an only child, access to outdoor spaces at home, having pets, and parents informing their children about the pandemic using creative explanations. Conclusions: During strict home confinement, a considerable emotional impact was observed in children as described by their parents. Specific elements were associated with a better or poorer emotional state.

Computational Model for Electrochemical Surface-Enhanced Raman Scattering: Key Role of the Surface Charges and Synergy between Electromagnetic and Charge-Transfer Enhancement Mechanisms.

We present a computational model for electrochemical surface-enhanced Raman scattering (EC-SERS). The surface excess of charge induced by the electrode potential (Vel) was introduced by applying an external electric field to a set of clusters [Agn]q with (n, q) of (19, ±1) or (20, 0) on which a molecule adsorbs. Using DFT/TD-DFT calculations, these metal-molecule complexes were classified by the adsorbate partial charge, and the main Vel-dependent properties were simultaneously studied with the aid of vibronic resonance Raman computations, namely, changes on the vibrational wavenumbers, relative intensities, and enhancement factors (EFs) for all SERS mechanisms: chemical or nonresonant, and resonance Raman with bright states of the adsorbate, charge-transfer (CT) states, and plasmon-like excitations on the metal cluster. We selected two molecules to test our model, pyridine, for which Vel has a remarkable effect, and 9,10-bis((E)-2-(pyridin-4-yl)vinyl)anthracene, which is almost insensitive to the applied bias. The results nicely reproduced most of the experimental observations, while the limitations of our approach were critically evaluated. We detected that accounting explicitly for the surface charges is key for EC-SERS models and that the highest calculated EFs, up to 107 to 108, are obtained by interstate coupling of bright local excitations of the metal cluster and CT states. These results highlight the importance of nonadiabatic effects in SERS and the capabilities of EC-SERS as a technique with potential to study excited-state coupling by tuning the CT and plasmon-like states by manipulating Vel.

Correlation between MAMMI-PET findings and anatomopathological outcomes in breast cancer patients.

OBJECTIVE: Imaging tests are a key element in the preoperative diagnosis of patients with breast cancer. Whole-body PET-computed tomography (PET/CT) breast studies have a limited spatial resolution, although dedicated breast PET (dbPET) devices such as the Mammography with Molecular Imaging PET (MAMMI-PET), have an increased sensitivity to detect tumor foci, especially those smaller than 2 cm. The purpose of this study is to define the validity and reliability of this new device. METHODS: A prospective and analytical observational study was carried out in a sample of patients with histologically confirmed breast cancer who were treated at our hospital between January 2017 and November 2018. The anatomopathological study findings for the surgical pieces were used as gold standards and we calculated their concordance with the findings from the MAMMI-PET as well as the validity and reliability parameters for this test. RESULTS: Data from 32 patients and 44 lesions (36 malignant and 8 benign) were evaluated. The mean patient age was 51.50 ± 11.68 years. Twenty patients had received neoadjuvant chemotherapy (NACT). The technique concordance rate was weak ( K = 0.349, P = 0.001) and was 84.3% for benign lesions and 62.6% for malignant ones. The MAMMI-PET sensitivity was 75%, whereas its specificity was 57.1%; the positive predictive value was 81.8% and the negative predictive value was 47.1%, with an overall precision of 70%. The MAMMI-PET sensitivity was higher in patients who had not undergone NACT and was significantly higher in patients with luminal B breast cancer compared to the luminal A subtype. CONCLUSION: The MAMMI-PET device had acceptable sensitivity and a high positive predictive value for the preoperative evaluation of patients with breast cancer; it was especially useful for lesions whose diagnosis with other imaging tests had been doubtful.