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The constant passage of trains on the railways tracks causes, in the course of time, deviations that must be corrected periodically by means of a track calibration process. It consists of designing a new layout, called recreated horizontal alignment (RHA), as close as possible to the deformed center track fulfilling also the technical constraints according to the operational requirements of the railway. In recent years, different models have been proposed to address this task. This paper proposes, first, a new geometrical model that works with continuous variables for the definition of horizontal alignments (HAs) to deal with nonsymmetric transition curves at both sides of a circular curve and second, an optimization algorithm to compute the recreated alignment suitable in sinuous railway sections. This new mathematical model frees the optimization process from the need to previously identify the geometric elements (tangents, circular curves, and transition curves) of the HA. The usefulness of this model is tested with two academic examples showing its good behavior and in a real case study, where this algorithm is compared with the solution adopted by the engineers in a section of the railway line Ourense–Monforte in the NW of Spain.

Background: In 1973, Saunders T. Frank described the diagonal earlobe crease (DELC) as a potential marker of cardiovascular disease. However, this anatomical finding is not routinely examined. The aim of this study was to assess the presence of this crease in the general population attending a dental setting and describe its anatomical variations to be able to categorize it as a physical sign. Methodology: A study group of 1050 white adults were selected, as participants in the framework of the "A Estrada Study of Glycation and Inflammation" (AEGIS), a cross-sectional, population-based descriptive study of a representative sample of the general adult population of the municipality of A Estrada (Pontevedra, Spain). Each participant's age, sex, and preferred head position when sleeping were recorded. Both earlobes were visually inspected and the anatomical variables of the crease were recorded (unilateral or bilateral, length, depth, and presence of secondary creases). The relationship between the study variables was analyzed using the chi-squared test, Student's t-test, the analysis of variance (ANOVA), and the nonparametric tests of Mann-Whitney and Kruskal-Wallis. Results: The DELC was observed in 65.2% of the participants. In 71.5% of the cases, the sign was complete (occupying the space from the tragus to the posterior edge of the earlobe); in 56.9% of the cases, the sign was bilateral; in 45.1% of the cases it was deep; and in the 43.6% of the cases, accessory creases were identified. Neither sex nor the habitual head position when sleeping were related to the prevalence or characteristics of the DELC. The prevalence, extent and depth of Frank's sign increased significantly with age (p < .001). Conclusion: The prevalence of the DELC increases significantly with age, and its morphological characteristics are accentuated. This finding, therefore, gains special relevance as a marker of potential cardiovascular disease when observed in young adults

A range of densely functionalized ullazines have been synthesized by a one-pot Rh(III)-catalyzed twofold C-H activation/oxidative annulation of N-arylpyrroles with alkynes. Electrophilic bromination at 5- or 5,7- positions of the EWG-substituted ullazine core offers an interesting single or double entry for further extended functionalization. Mechanistic considerations suggest two complementary paths, EWG-assisted and SEAr, for the C-H activations. All ullazines exhibit strong fluorescence emissions. Ullazines bearing thiophene and triarylamine units at 5- and 5,7- positions show a significant bathochromic shift in their emission spectra, attributed to the more extended electronic circuits present.

Background: The prevalence of cancer patients with concomitant cardiovascular (CV) disease is on the rise due to improved cancer prognoses. The aim of this study is to evaluate the long-term outcomes of cancer patients referred to a cardiology department (CD) via primary care using e-consultation. Methods: We analysed data from cancer patients with prior referrals to a CD between 2010 and 2021 (n = 6889) and compared two care models: traditional in-person consultations and e-consultations. In e-consultation model, cardiologists reviewed electronic health records (e-consultation) to determine whether the demand could be addressed remotely or necessitated an in-person consultation. We used an interrupted time series regression model to assess outcomes during the two periods: (1) time to cardiology consultation, (2) rates of all-cause and CV related hospital admissions and (3) rates of all-cause and CV-related mortality within the first year after the initial consultation or e-consultation at the CD. Results: Introduction of e-consultation for cancer patients referred to cardiology care led to a 51.8% reduction (95%CI: 51.7%–51.9%) in waiting times. Furthermore, we observed decreased 1-year incidence rates, with incidence rate ratios (iRRs) [IC95%] of .75 [.73–.77] for CV-related hospitalizations, .43 [.42–.44] for all-cause hospitalizations, and .87 [.86–.88] for all-cause mortality. Conclusions: Compared to traditional in-person consultations, an outpatient care program incorporating e-consultation for cancer patients significantly reduced waiting times for cardiology care and demonstrated safety, associated with lower rates of hospital admissions

This study addresses the fabrication of microporous plasmonic nanocomposites (NCs) by using plasmonic nanoparticles (i.e., gold bipyramids, AuB) as seeds to grow microporous shells, specifically, metal–organic frameworks (MOF) PCN-224 of increasing thickness from 69 to 138 nm. This method is based on using a previously synthesized Zr6-oxo cluster and unfolds at room temperature. Notably, it is demonstrated that the concentration of the AuB seeds determines both the yield of NCs and the resultant thickness of the PCN-224 shell, illustrating the seeded growth mechanism. Furthermore, it is found that the thermoplasmonic response of the NCs is dominated by the thickness of the microporous shell, with thicker shells having enhanced thermal confinement properties than thinner ones. As a proof of concept, the NCs are loaded with cresyl violet (CV), a lysosomal fluorescent marker. This serves to demonstrate the thermoplasmonic-induced intracellular release of CV by the photostimulation of the AuB's plasmonic near-infrared (NIR) band. Moreover, the NCs display exceptional efficacy as photodynamic agents when photostimulated at the PCN-224's Soret band. In summary, this study offers a facile, efficient, and reproducible methodology for the fabrication of NCs with a controlled geometry while unlocking new possibilities in the field of nanoMOFs as multifunctional theranostic probes.

Aim To assess the relative relevance of dispersal limitation and species sorting as drivers of spatial turnover between spider faunas of European territories. Location Continental Europe. Time period Present. Major taxa studied Spiders (Order Araneae). Methods We analysed how distance-decay patterns differ between northern and southern Europe (broadly, territories covered vs. not covered by ice sheets during the last glacial maximum, respectively) in 15 spider families, using standardized distances to allow a direct comparison between parameters (i.e. slope and intercept) of climatic and spatial distance-decay models. Thus, we assessed North–South differences in parameters of spatial and, independently, climatic distance-decay models, and whether those differences are explained by family-specific traits related to dispersal ability. Results Climatic and spatial distance-decay patterns are very similar in northern Europe, where climatic and spatial distances are highly correlated. In contrast, slopes are steeper in spatial than in climatic distance-decay curves in southern Europe, where climatic and spatial distances are decoupled. Moreover, family traits related to dispersal ability explained the North–South difference in spatial distance-decay slopes, as well as the amount of nestedness-resultant dissimilarity between southern and northern spider faunas. Main conclusions Our results suggest that differences in beta diversity patterns between northern and southern Europe reflect the strength of dispersal limitation in spiders, which varies across families and leads to different degrees of disequilibrium with current climatic conditions depending on the taxon. Moreover, in the South of Europe, where spatial and climatic distances are uncorrelated, spatial distance-decay models are steeper and have larger explanatory power than climatic distance-decay models, which suggests that dispersal limitation is the main factor shaping current beta diversity patterns of Europea

Unified models of biological diversity across organizational levels (genes, species, communities) provide key insight into fundamental ecological processes. Theory predicts that the strength of the correlation between species abundance and genetic diversity should be related to community age in closed communities (i.e. abundant species accumulate more genetic diversity over time than rare species). Following this rationale, we hypothesize that historical climatic events are expected to impact assembly processes, hence affecting both the species abundance distribution (SAD) and the species genetic distribution (SGD) in continental communities. Therefore, we predict that, if the congruence between SADs and SGDs depends on community age, then higher congruence would be observed in localities where climate has been more stable since the Last Glacial Maximum (LGM). We tested this prediction using relative abundance and nucleotide diversity (cox1-5′) data from 20 communities of leaf beetles along a latitudinal transect in the Iberian Peninsula. We observed that the congruence between SAD and SGD curves, measured as the correlation between the species' rank orders in both distributions, was significantly related to the change in mean annual temperature since the LGM, but not to current climatic conditions. Our results suggest that, despite the high connectivity of continental communities, historical climatic stability is still a relevant predictor of the congruence between species abundance and genetic diversity. Hence, the degree of congruence between SADs and SGDs could be used as a proxy of community stability, related not only to historical climatic variation but also to any other disrupting factors, including human pressure.

The lack of selectivity toward the oxygen reduction reaction (ORR) in metal nanoparticles can be linked to the generation of intermediates. This constitutes a crucial constraint on the performance of specific electrochemical devices, such as fuel cells and metal–air batteries. To boost selectivity of metal nanoparticles, a novel methodology that harnesses the unique electrocatalytic properties of polyoxometalates (POM) to scavenge undesired intermediates of the ORR (such as HO2−) promoting selectivity is proposed. It involves the covalent functionalization of metal nanoparticle's surface with an electrochemically active capping layer containing a new sulfur-functionalized vanadium-based POM (AuNP@POM). To demonstrate this approach, preformed thiolate Au(111) nanoparticles with a relatively poor ORR selectivity are chosen. The dispersion of AuNP@POM on the surface of carbon nanofibers (CNF) enhances oxygen diffusion, and therefore the ORR activity. The resulting electrocatalyst (AuNP@POM/CNF) exhibits superior stability against impurities like methanol and a higher pH tolerance range compared to the standard commercial Pt/C. The work demonstrates for the first time, the use of a POM-based electrochemically active capping layer to switch on the selectivity of poorly selective gold nanoparticles, offering a promising avenue for the preparation of electrocatalyst materials with improved selectivity, performance, and stability for ORR-based devices.

The Environmental Kuznets Curve (EKC) hypothesis has become an important topicin the literature on the effects of growth on the environment, albeit surrounded bysome controversy and nuance. Although this hypothesis has been analyzed in the lit-erature in multiple ways and using different variables, there is still a gap in the consid-eration of global value chains (GVCs), which delve into the international division ofproduction. This is particularly important in the intermediate stages of production, asthey include tasks with a greater environmental impact. This research aims to analyzethe environmental effects of economic growth and foreign trade linked to GVCs in asample of 12 countries of East and Southeast Asia, given their strong insertion inGVCs. Based on the EKC, variables such as GDP per capita, environmental impact,and renewable energy consumption are incorporated. As a novelty, the research alsoincludes GVCs participation and position indexes, and different measures of CO2emissions. Our results confirm the existence of a nonlinear relationship between eco-nomic activity and its environmental effects, although with important nuancesdepending on the mode of insertion of each country in GVCs. In this sense, althoughall the selected countries increased their total emissions, substantial disparities areobserved depending on the perspective considered (producer, consumer, andexports). Ultimately, it is concluded that, for an effective reduction of the environ-mental impact in these countries, it is essential to design policy measures, targetingnew technologies, consumption and production patterns, and attracting green foreigndirect investment

The on-chip extraction of dynamic information from a scene can be addressed with either frame-based CMOS vision, also called smart image sensors, or dynamic vision sensors, also known as event cameras. When implemented with a pinned photodiode (PPD) as a 4-transistor active pixel sensor (4T-APS), the former brings about the benefits of low temporal noise and dark current but without high dynamic range (HDR). The latter comes with the benefits of HDR and a fast event detection rate with low power consumption. The drawback is the background activity noise, which leads to additional hardware or algorithms to keep it low. This paperanalyses the mismatch and noise of a global shutter 4T-APS implementation with local HDR through an overflow capacitor and correlated double sampling (CDS) to provide low noise events through frame differencing. The aim is to narrow the gap with dynamic vision sensors in terms of event rate and dynamic range. We show that our solution would be competitive with event cameras in scenarios with slow moving objects and a relatively wide dynamic range (85 dB).

Aims: The objective of this study was to develop a new website in Spanish on oral health and dental care for use by the relatives/caregivers of individuals with Down syndrome, with the aim of incorporating the strengths and avoids the deficiencies of existing websites. Methods: A freely accessible website was developed with dental content, whose access criteria included the age of the individual undergoing the consultation and the area of interest (tongue or teeth disease, oral functionality, oral hygiene, and dental visits). The definitive version of the website was analyzed by five external examiners, applying the DISCERN criteria and the Questionnaire to Evaluate Health Web Sites According to European Criteria (QEEC). The website's traffic during the first year of activity was recorded. Results: The new website is known as “DentiDown”, and its access domain is https://odontoloxia accessible.org/dentidown/. On the home screen, the age group of interest to the user can be accessed. A dropdown menu then opens, listing the various options according to the area of interest. The oral hygiene section provides advice for improving toothbrushing efficacy through demonstration videos. With the DISCERN tool, an overall score of 4.75 ± 0.5 was achieved. With the QEEC, the external examiners’ general opinion was highly favorable. The website received the seal of quality from the Accredited Medical Web (AMW). During the first year of activity, a total of 4536 visits from a total of 45 countries were recorded. Conclusion: A new Spanish website has been developed on oral health for use by the relatives/caregivers of individuals with Down syndrome. The website has been favorably evaluated by external experts and, to date, is the only one with these characteristics with the AMW seal of quality

The relationship between Environmental Social and Governance (ESG) activities and financial performance has been explored within large companies. The presence of these activities in Small and Medium Enterprises (SMEs) is still in its early stages in the literature, requiring further empirical evidence. Given the importance of SMEs in economy and based on Stakeholder Theory, a set of hypotheses regarding the influence of ESG on financial and risk performance has been tested using a sample of 538 Spanish SMEs. Specifically, an index has been developed to assess ESG at both global and individual levels. The study analyses the impact of these variables on corporate performance, taking into account factors such as the pandemic period, level of disclosure and the size effect. The results demonstrate the importance of developing and index tailored to measuring ESG within this type of company, as the methodology employed can impact the outcomes. Moreover, at the individual level, all dimensions reflect a significant relationship, but the overall ESG score does not. The social and labor dimensions prove to be the most beneficial indices for enhancing resilience during periods of crisis. Finally, the findings confirm that it is more difficult for SMEs to monetize the results of ESG investment and that disclosing these activities has a positive impact. This study contributes to existing knowledge by constructing a robust measure of the level of ESG implementation and quality, providing valuable insights for SMEs on how to effectively manage their ESG activities

Wolves, akin to their fellow canids, extensively employ chemical signals for various aspects of communication, including territory maintenance, reproductive synchronisation and social hierarchy signalling. Pheromone-mediated chemical communication operates unconsciously among individuals, serving as an innate sensory modality that regulates both their physiology and behaviour. Despite its crucial role in the life of the wolf, there is a lacuna in comprehensive research on the neuroanatomical and physiological underpinnings of chemical communication within this species. This study investigates the vomeronasal system (VNS) of the Iberian wolf, simultaneously probing potential alterations brought about by dog domestication. Our findings demonstrate the presence of a fully functional VNS, vital for pheromone-mediated communication, in the Iberian wolf. While macroscopic similarities between the VNS of the wolf and the domestic dog are discernible, notable microscopic differences emerge. These distinctions include the presence of neuronal clusters associated with the sensory epithelium of the vomeronasal organ (VNO) and a heightened degree of differentiation of the accessory olfactory bulb (AOB). Immunohistochemical analyses reveal the expression of the two primary families of vomeronasal receptors (V1R and V2R) within the VNO. However, only the V1R family is expressed in the AOB. These findings not only yield profound insights into the VNS of the wolf but also hint at how domestication might have altered neural configurations that underpin species-specific behaviours. This understanding holds implications for the development of innovative strategies, such as the application of semiochemicals for wolf population management, aligning with contemporary conservation goals

Background Studies on vaccine effectiveness (VE) against COVID-19 in the pediatric population are outgoing. We aimed to quantify VE against SARS-CoV-2 in two pediatric age groups, 5–11 and 12–17-year-old, while considering vaccine type, SARS-CoV-2 variant, and duration of protection. Methods A population-based test-negative control study was undertaken in Galicia, Spain. Children 5–11-year-old received the Comirnaty® (Pfizer, US) vaccine, while those aged 12–17-year-old received the Comirnaty® (Pfizer, US) or SpikeVax® (ModernaTX, Inc) vaccine. Participants were categorized into unvaccinated (0 doses or one dose with <14 days since vaccination), partially vaccinated (only one dose with ≥14 days, or two doses with <14 days after the second dose administration), and fully vaccinated (two doses with ≥14 days after the second injection). Adjusted odds ratios (OR) and their 95% confidence intervals (CI) were estimated using multiple logistic regression models. VE was calculated as (1-OR) * 100. Stratified and sensitivity analyses were performed. Results In the fully vaccinated 5–11-year-old children, VE against the Omicron variant was 44.1% (95% CI: 38.2%–49.4%). In the fully vaccinated 12–17-year-old individuals, VE was 83.4% (95% CI: 81.2%–85.3%) against Delta and 74.8% (95% CI: 58.5%–84.9%) against Omicron. Comirnaty® and SpikeVax® vaccines showed a similar magnitude of VE against Delta [Comirnaty® VE: 81.9% (95% CI: 79.3%–84.1%) and SpikeVax® VE: 85.3% (95% CI: 81.9%–88.1%)]. Comirnaty® (Pfizer, US; VE: 79.7%; 95% CI: 50.7%–92.4%) showed a slightly higher magnitude of protection against Omicron than SpikeVax® (ModernaTX, Inc), yet with an overlapping CI (VE: 74.3%; 95% CI: 56.6%–84.9%). VE was maintained in all age subgroups in both pediatric populations, but it declined over time. Conclusions In Galicia, mRNA VE was moderate against SARS-CoV-2 infections in the 5–11-year-old populations, but high in older children. VE declined over time, suggesting a potential need

Despite the impressive advances in the synthesis of atomically precise graphene nanostructures witnessed during the last decade, advancing in compositional complexity faces major challenges. The concept of introducing the desired functional groups or dopants in the molecular precursor often fails due to their lack of stability during the reaction path. Here, a study on the stability of different pyridine and pyrimidine moieties during the on-surface synthesis of graphene nanoribbons on Au(111) is presented. Combining bond-resolved scanning tunneling microscopy with X-ray photoelectron spectroscopy, the thermal evolution of the nitrogen dopants throughout the whole reaction sequence is tracked. A comparative experimental and ab initio electronic characterization confirms the presence of dopants in the final structures, revealing also that the pyridinic nitrogen leads to a significant band downshift. The results demonstrate that, by using synthetic strategies to lower the reaction temperatures, one can preserve specific N-heterocycles throughout all the reaction steps of the synthesis of graphene nanoribbons and beyond the interibbon coupling reaction that leads to nanoporous graphene

Catalytic water splitting is a promising approach to produce clean hydrogen fuel from renewable energy sources. However, developing hybrid heterostructures capable of efficiently breaking down water into its constituent elements, hydrogen, and oxygen, presents a considerable challenge. In this study, a novel hierarchical POM/Pd/MoS2 hybrid heterostructure, composed of sheets of MoS2 modified with Pd nanoparticles and combined with a cobalt-based polyoxometalate (POM), serving as bifunctional catalyst for water splitting is reported. Through a synergistic synthetic approach, MoS2, acting as a reducing agent, triggers the nucleation and growth of Pd nanoparticles, which, in turn, serve as anchoring sites for the polymerization of the cobalt-based POM into fibers. POM/Pd/MoS2 hybrid exhibits an enhanced oxygen evolution reaction (OER) activity, comparable to the benchmark catalysts Ir/C and IrO2/C in alkaline media, being its hydrogen evolution reaction (HER) activity similar to the activated Pd/MoS2 hybrid. The intriguing electrocatalytic capability of the resulting material for producing hydrogen and oxygen through electrochemical means arises from the enhanced charge storage capacity and conductivity of MoS2, the multi-electron transfer facilitated by the POM, and the high electrocatalytic activity of the metals

The success of personalized medicine in oncology relies on using highlyeffective and precise therapeutic modalities such as small interfering RNA(siRNA) and monoclonal antibodies (mAbs). Unfortunately, the clinicalexploitation of these biological drugs has encountered obstacles inovercoming intricate biological barriers. Drug delivery technologies representa plausible strategy to overcome such barriers, ultimately facilitating theaccess to intracellular domains. Here, an overview of the current landscapeon how nanotechnology has dealt with protein corona phenomena as a firstand determinant biological barrier is presented. This continues with theanalysis of strategies facilitating access to the tumor, along with conceivablemethods for enhanced tumor penetration. As a final step, the cellular barriersthat nanocarriers must confront in order for their biological cargo to reachtheir target are deeply analyzed. This review concludes with a critical analysisand future perspectives of the translational advances in personalizedoncological nanomedicine

Low-valent cobalt complexes equipped with phosphorous type of ligands can promote the intramolecular (3+2) cycloaddition of alkylidenecyclopropanes (ACPs) with alkenes and with allenes. Dienes can also be used as partners, but they afford seven-membered cycloadducts. The reactions are fully diastereoselective and, in some cases, we also observed moderate enantioselectivities, especially when using chiral phosphite ligands.

One-dimensional selective NMR experiments relying on a J-filter element are proposed to isolate specific signals in crowded 1H spectral regions. The J-filter allows the edition or filtering of signals in a region of interest of the spectrum by exploiting the specific values of their 1H-1H coupling constants and certain parameters of protons coupled to them that appear in less congested parts of the spectrum (chemical shifts and coupling constants). The new experiments permitted the isolation of specific peaks of phytosterol components in a sample obtained from a liquid nutraceutical recommended for lowering blood cholesterol levels in regions with complete overlap in the 1H spectrum.

Life insurance enhances households' capacity to absorb financial shocks and protects against personal risks that no one likes to contemplate. This is even more important in times of economic hardship such as now, when many Europe countries and particularly Spain are going through difficult times due to rising inflation, the war in Ukraine, and the ongoing COVID-19 pandemic. Although previous studies have analysed the driving forces of life insurance demand, the influence of the individual's financial planning horizon, financial knowledge, and financial self-control have been underexplored. This study analyses the influence of personal financial attributes on life insurance demand and, in so doing, explores whether the effects of such attitudes differ across different generational cohorts (i.e., the silent generation, baby boomers, Gen Xers, and millennials). The data, taken from the Survey of Financial Competences, comprises 7245 Spanish individuals. Evidence from multivariate analyses reflects the relevance of standard sociodemographic characteristics in explaining individuals' decisions to become life insurance holders. In contrast, evidence does not support a statistically significant relationship in the case of behavioural variables such as financial self-control and the financial planning horizon

Triangulenes are a class of open-shell triangular graphene flakes with total spin increasing with their size. In the last years, on-surface-synthesis strategies have permitted fabricating and engineering triangulenes of various sizes and structures with atomic precision. However, direct proof of the increasing total spin with their size remains elusive. In this work, we report the combined in-solution and on-surface synthesis of a large nitrogen-doped triangulene (aza-[5]-triangulene) on a Au(111) surface, and the detection of its high-spin ground state. Bond-resolved scanning tunneling microscopy images uncovered radical states distributed along the zigzag edges, which were detected as weak zero-bias resonances in scanning tunneling spectra. These spectral features reveal the partial Kondo screening of a high-spin state. Through a combination of several simulation tools, we find that the observed distribution of radical states is explained by a quintet ground state (S=2), instead of the quartet state (S=3/2) expected for the neutral species. This confirms that electron transfer to the metal substrate raises the spin of the ground state. We further provide a qualitative description of the change of (anti)aromaticity introduced by N-substitution, and its role in the charge stabilization on a surface, resulting in an S=2 aza-triangulene on Au(111)

Treatment failure in breast cancers overexpressing human epidermal growth factor receptor 2 (HER2) is associated mainly to the upregulation of human epidermal growth factor receptor 3 (HER3) oncoprotein linked to chemoresitence. Therefore, to increase patient survival, here a multimodal theranostic nanoplatform targeting both HER2 and HER3 is developed. This consists of doxorubicin-loaded branched gold nanoshells functionalized with the near-infrared (NIR) fluorescent dye indocyanine green, a small interfering RNA (siRNA) against HER3, and the HER2-specific antibody Transtuzumab, able to provide a combined therapeutic outcome (chemo- and photothermal activities, RNA silencing, and immune response). In vitro assays in HER2+/HER3+ SKBR-3 breast cancer cells have shown an effective silencing of HER3 by the released siRNA and an inhibition of HER2 oncoproteins provided by Trastuzumab, along with a decrease of the serine/threonine protein kinase Akt (p-AKT) typically associated with cell survival and proliferation, which helps to overcome doxorubicin chemoresistance. Conversely, adding the NIR light therapy, an increment in p-AKT concentration is observed, although HER2/HER3 inhibitions are maintained for 72 h. Finally, in vivo studies in a tumor-bearing mice model display a significant progressively decrease of the tumor volume after nanoparticle administration and subsequent NIR light irradiation, confirming the potential efficacy of the hybrid nanocarrier

Dynamic P/M (plus/minus) helical memory in chiral dissymmetric poly(diphenylacetylene)s (PDPA) is shown using a PDPA that bears the benzamide of (L)-alanine methyl ester as pendant. For a single chiral polymer, it is possible to obtain either P or M helical structures in a specific solvent without the presence of any chiral external stimuli. To do that, it is necessary to combine the conformational control at the pendant group with a high steric hindrance at the backbone. In this case, by thermal annealing in low-polar solvents, an anti-conformer is stabilized at the pendant which commands a P helix in the PDPA. Next, solvent removal followed by addition of a polar solvent such as dimethyl sulfoxide (DMSO), results in the kinetic conformationally trapped P helix. However, in this medium, the preferred handedness and the thermodynamic macromolecular helix for poly-(L)-1 is M. This process also occurs in the opposite way. Electronic circular dichroism (ECD) and circularly polarized luminescence (CPL) studies show that the dynamic memory effect is present both in ground and excited states

Objective To describe a method to calculate the total intra-articular volume (inter-osseous space) of the temporomandibular joint (TMJ) determined by cone-beam computed tomography (CBCT). This could be used as a marker of tissue proliferation and different degrees of soft tissue hyperplasia in juvenile idiopathic arthritis (JIA) patients. Materials and Methods Axial single-slice CBCT images of cross-sections of the TMJs of 11 JIA patients and 11 controls were employed. From the top of the glenoid fossa, in the caudal direction, an average of 26 slices were defined in each joint (N = 44). The interosseous space was manually delimited from each slice by using dedicated software that includes a graphic interface. TMJ volumes were calculated by adding the areas measured in each slice. Two volumes were defined: Ve−i and Vi, where Ve−i is the inter-osseous space, volume defined by the borders of the fossa and Vi is the internal volume defined by the condyle. An intra-articular volume filling index (IF) was defined as Ve−i/Vi, which represents the filling of the space. Results The measured space of the intra-articular volume, corresponding to the intra-articular soft tissue and synovial fluid, was more than twice as large in the JIA group as in the control group. Conclusion The presented method, based on CBCT, is feasible for assessing inter-osseus joint volume of the TMJ and delimits a threshold of intra-articular changes related to intra-articular soft tissue proliferation, based on differences in volumes. Intra-articular soft tissue is found to be enlarged in JIA patients

In the last 20 years, immediate implant placement has been proposed as a predictable protocol to replace failing teeth. The research conducted in preclinical and clinical studies have focused on soft and hard tissue changes following tooth extraction and immediate implant placement. Different approaches for hard and soft tissue grafting together with provisional restorations have been proposed to compensate tissue alterations. This review analyzed some relevant clinical and preclinical literature focusing on the impact of bone grafting procedures on immediate implant placement in terms of hard and soft tissue changes, aesthetic results, and patient-related outcomes

In this work, 124 samples of slurry from 32 commercial farms of three animal categories (lactating sows, nursery piglets, and growing pigs) were studied. The samples were collected in summer and winter over two consecutive years and analyzed for physicochemical properties, macronutrient and micronutrient, heavy metals, and major microbiological indicators. The results were found to be influenced by farm type and to deviate especially markedly in nursery piglets, probably as a consequence of differences in pig age, diet, and management. The main potential hazards of the slurries can be expected to arise from their high contents in heavy metals (Cu and Zn), especially in the nursery piglet group, and from the high proportion of samples testing positive for Salmonella spp. (66%). Linear and nonlinear predictive equations were developed for each animal category and the three as a whole. Dry matter, which was highly correlated with N, CaO, and MgO contents, proved the best predictor of fertilizer value. Using an additional predictor failed to improve the results but nonlinear and farm-specific equations did. Rapid on-site measurements can improve the accuracy of fertilizer value estimates and help optimize the use of swine slurry as a result

Clostridium luticellarii is a recently discovered acetogen that is uniquely capable of producing butyric and isobutyric acid from various substrates (e.g. methanol), but it is unclear which factors influence its (iso)butyric acid production from H2 and CO2. We aimed to investigate the autotrophic metabolism of C. luticellarii by identifying the necessary growth conditions and examining the effects of pH and metabolite levels on product titers and selectivity. Results show that autotrophic growth of C. luticellarii requires the addition of complex nutrient sources and the absence of shaking conditions. Further experiments combined with thermodynamic calculations identified pH as a key parameter governing the direction of metabolic fluxes. At circumneutral pH (~6.5), acetic acid is the sole metabolic end product but C. luticellarii possesses the unique ability to co-oxidize organic acids such as valeric acid under high H2 partial pressures (>1 bar). Conversely, mildly acidic pH (≤5.5) stimulates the production of butyric and isobutyric acid while partly halting the oxidation of organic acids. Additionally, elevated acetic acid concentrations stimulated butyric and isobutyric acid production up to a combined selectivity of 53 ± 3%. Finally, our results suggest that isobutyric acid is produced by a reversible isomerization of butyric acid, but valeric and caproic acid are not isomerized. These combined insights can inform future efforts to optimize and scale-up the production of valuable chemicals from CO2 using C. luticellarii

In this article, we investigate the estimation of the transient mold-slab heat flux in continuous casting molds given some thermocouples measurements in the mold plates. Mathematically, we can see this problem as the estimation of a Neumann boundary condition given pointwise state observations in the interior of the domain. We formulate it in a deterministic inverse problem setting. After introducing the industrial problem, we present the mold thermal model and related assumptions. Then, we formulate the boundary heat flux estimation problem in a deterministic inverse problem setting using a sequential approach according to the sequentiality of the temperature measurements. We consider different formulations of the inverse problem. For each one, we develop novel direct methodologies exploiting a space parameterization of the heat flux and the linearity of the mold model. We construct these methods to be divided into a computationally expensive offline phase that can be computed before the process starts, and a cheaper online phase to be performed during the casting process. To conclude, we test the performance of the proposed methods in two benchmark cases

Recent years have witnessed a considerable progress in research aimed at merging transition metal catalysis with chemical and cell biology. Therefore, a crescent number of metal-catalyzed transformations have been shown compatible with biological media and even with living settings. Of the different transition metals used to build these biocompatible catalysts, ruthenium has demonstrated to be particularly powerful, in part because the resulting complexes exhibit a very good balance between reactivity and biological stability. Indeed, ruthenium complexes have demonstrated utility to promote a great variety of reactions in biologically relevant contexts, from deprotection and redox processes to cycloadditions or photocatalytic transformations. Many of these reactions may enable the development of new type of biological tools and pharmacological strategies

Sustainability is a major challenge in today's business world, making environmental,social and governance criteria an indispensable tool for business management andinvestment decisions. Using 2020 data of 47 companies from the STOXX EuropeTotal Market Utilities Index and qualitative comparative analysis, this study aims toanalyse how the combination of CO2equivalent emissions, sustainability compensa-tion incentives, environmental investments, environment management training, andpolicy fair competition leads to utility companies' stock market returns. Two subsam-ple models (electricity and non‐electricity utilities) have been considered in the study.The results point to the absence of CO2equivalent emissions, the absence of incen-tives, and the presence of environmental investment as key variables to lead to stockmarket returns. The findings provide relevant information for managers and practi-tioners of utilities industry to achieve improvements in the environmental, social andgovernance management practices, maintaining profitability in financial markets andfacilitating decision‐making for investors

Working capital management (WCM) is a critical matter forthe growth of firms, especially small and medium‐sizedmanufacturing companies faced with liquidity shortageswhose current assets account for a significant part of theirinvestments. These characteristics describe most compa-nies in the fish processing industry. Using a sample of morethan 1050 European fish processing companies duringthe period 2013–2020 and applying dynamic panel datamethods, this paper analyses the extent to which workingcapital investment and financing policies affect firm's salesgrowth. The empirical evidence reveals that the trade creditchannel (i.e., accounts receivable and accounts payable)enhances sales growth, while the opposite effect is foundfor investment in inventories. Additionally, the findingsinsist on the importance of financing current assets withpositive working capital to boost sales growth. [EconLitCitations: C23, G31, L25, L79, Q22]

Chiral information transmission in helical polymers bearing multi-chiral pen-dant groups is usually determined by the absolute configuration of the first chi-ral center. The second chiral residue usually has low-to-null influence in themacromolecular handedness of the polymer, due to its remote position respectto the polyene main chain. Here, we demonstrate how the stimuli responsiveproperties of diastereomeric polymers, obtained by changing the absolute con-figuration of the second chiral center, are different due to the unlike propertiesof diastereoisomers

Light detection and ranging (LiDAR) scanning in urban environments leads to accurate and dense three-dimensional point clouds where the different elements in the scene can be precisely characterized. In this paper, two LiDAR-based algorithms that complement each other are proposed. The first one is a novel profiling method robust to noise and obstacles. It accurately characterizes the curvature, the slope, the height of the sidewalks, obstacles, and defects such as potholes. It was effective for 48 of 49 detected zebra crossings, even in the presence of pedestrians or vehicles in the crossing zone. The second one is a detailed quantitative summary of the state of the zebra crossing. It contains information about the location, the geometry, and the road marking. Coarse grain statistics are more prone to obstacle-related errors and are only fully reliable for 18 zebra crossings free from significant obstacles. However, all the anomalous statistics can be analyzed by looking at the associated profiles. The results can help in the maintenance of urban roads. More specifically, they can be used to improve the quality and safety of pedestrian routes

Iridium-catalyzed borylations of aromatic C−H bonds are highly attractive transformations because of the diversification possibilities offered by the resulting boronates. These transformations are best carried out using bidentate bipyridine or phenanthroline ligands, and tend to be governed by steric factors, therefore resulting in the competitive functionalization of meta and/or para positions. We have now discovered that a subtle change in the bipyridine ligand, namely, the introduction of a CF3 substituent at position 5, enables a complete change of regioselectivity in the borylation of aromatic amides, allowing the synthesis of a wide variety of ortho-borylated derivatives. Importantly, thorough computational studies suggest that the exquisite regio- and chemoselectivity stems from unusual outer-sphere interactions between the amide group of the substrate and the CF3-substituted aryl ring of the bipyridine ligand

Research on consumer financial vulnerability (CFV) was especially encouraged in the aftermath of the 2007–2008 financial crisis, becoming a phenomenon of global interest to academics and policy makers. This paper reviews the existing academic literature on CFV with the aim of mapping out four research fields (i.e., the concept, the measures, the methods, and the drivers of this phenomenon) and providing a roadmap for a future research agenda for this field. To this end, we review the last two decades of academic research on households’ financial vulnerability, thereby presenting a hybrid literature review. Evidence from a comprehensive analysis of 98 academic papers suggests that this is still an emerging and highly fragmented field and, therefore, a comprehensive future research agenda is offered, including concrete suggestions for research designs and measurements. The proposal of a homogeneous definition of financial vulnerability, the consideration of measures that include subjective aspects of the phenomenon, the use of qualitative methods, and the development of more detailed theoretical and empirical research on the drivers of CFV, are among the authors’ recommendations for future research

Sex determination (SD) shows huge variation among fish and a high evolutionary rate, as illustrated by the Pleuronectiformes (flatfishes). This order is characterized by its adaptation to demersal life, compact genomes and diversity of SD mechanisms. Here, we assembled the Solea senegalensis genome, a flatfish of great commercial value, into 82 contigs (614 Mb) combining long- and short-read sequencing, which were next scaffolded using a highly dense genetic map (28,838 markers, 21 linkage groups), representing 98.9% of the assembly. Further, we established the correspondence between the assembly and the 21 chromosomes by using BAC-FISH. Whole genome resequencing of six males and six females enabled the identification of 41 single nucleotide polymorphism variants in the follicle stimulating hormone receptor (fshr) consistent with an XX/XY SD system. The observed sex association was validated in a broader independent sample, providing a novel molecular sexing tool. The fshr gene displayed differential expression between male and female gonads from 86 days post-fertilization, when the gonad is still an undifferentiated primordium, concomitant with the activation of amh and cyp19a1a, testis and ovary marker genes, respectively, in males and females. The Y-linked fshr allele, which included 24 nonsynonymous variants and showed a highly divergent 3D protein structure, was overexpressed in males compared to the X-linked allele at all stages of gonadal differentiation. We hypothesize a mechanism hampering the action of the follicle stimulating hormone driving the undifferentiated gonad toward testis

Aims To assess the longer-term results (hospital admissions and mortality) in women versus men referred to a cardiology department from primary care using an e-consultation in our outpatient care programme. Methods We selected 61,306 patients (30,312 women and 30,994 men) who visited the cardiology service at least once between 2010 and 2021: 69.1% (19,997 women and 20,462 men) were attended in e-consultation (from 2013 to 2021) and 30.9% (8920 women and 9136 men) in in-person consultations (from 2010 to 2012) without gender differences in the proportion of patients attended in each period. Using an interrupted time series regression model, we analysed the impact of incorporating e-consultation into the healthcare model and evaluated the elapsed time to cardiology care, heart failure (HF), cardiovascular (CV), and all-cause hospital admissions and mortality during the one-year after cardiology consultation. Results The introduction of e-consultation substantially decreased waiting times to cardiology care; during the in-person consultation period, the mean delay for cardiology care was 57.9 (24.8) days in men and 55.8 (22.8) days in women. During the e-consultation period, the waiting time to cardiology care was markedly reduced to 9.41 (4.02) days in men and 9.46 (4.18) in women. After e-consultation implantation, there was a significant reduction in the 1-year rate of hospital admissions and mortality, both in women and men iRR [IC 95%]: 0.95 [0.93–0.96] for HF, 0.90 [0.89–0.91] for CV and 0.70 [0.69–0.71] for all-cause hospitalization; and 0.93 [0.92–0.95] for HF, 0.86 [0.86–0.87] for CV and 0.88 [0.87–0.89] for all-cause mortality in women; and 0.91 [0.89–0.92] for HF, 0.90 [0.89–0.91] for CV and 0.72 [0.71–0.73] for all-cause hospitalization; and 0.96 [0.93–0.97] for HF, 0.87 [95% CI: 0.86–0.87] for CV and 0.87 [0.86–0.87] for all-cause mortality, in men. Conclusion Compared with the in-person consultation period, an outpatient care programme that includes an e

The temporal concentration of snowfalls has direct implications on the management of water resources as well as on the economic activity of mountain areas, conditioning, for example, the seasonal performance of ski resorts. This work uses the daily concentration index (CI) for analysing the frequency concentration of snowfalls in the Iberian Peninsula Mountain ranges. First, we provide a spatiotemporal analysis of the CI patterns and trends for the 1980–2014 period. Subsequently, we determine the atmospheric circulation patterns that control the CI variability. In addition, we determine the geographical and low-frequency climate modes that control the CI for this mid-latitude area. In addition, we have estimated the partial dependence relationship between the CI and several geographical factors by fitting a multiple linear regression. The results from these analyses show that elevation as well as the distance from the Atlantic are the main geographical pattern that controls the CI in the Iberian Peninsula Mountain ranges. These geographical factors also reflect the role of the main atmospheric circulation patterns in the Iberian Peninsula in controlling the spatial dynamics of the CI. The Cantab rian, Iberian, and northern slopes of the Pyrenees show the lowest CI due to their exposition to northern and Atlantic circulation weather types. On the contrary, the highest CI values are found in the southern and eastern slopes of the Pyrenees, eastern slopes of Sierra Nevada, and southern slopes of the Central system. Trend analysis shows a slight increase of CI in the Central system and in the western Sierra Nevada. However, eastern Sierra Nevada, Cantabrian, Central, and Iberian show a downward CI trend. CI is principally driven by the East-Atlantic/Western Russia pattern and the North Atlantic Oscillation(NAO) in the Cantabrian, Iberian, and northern slopes of the Central range. The CI values in the Pyrenees show a different relationship with the Western Mediterranean

Employment of enzymes as biocatalysts offers immense benefits across diverse sectors in the context of green chemistry, biodegradability, and sustainability. When compared to free enzymes in solution, enzyme immobilization proposes an effective means of improving functional efficiency and operational stability. The advance of printable and functional materials utilized in additive manufacturing, coupled with the capability to produce bespoke geometries, has sparked great interest toward the 3-dimensional (3D) printing of immobilized enzymes. Printable biocatalysts represent a new generation of enzyme immobilization in a more customizable and adaptable manner, unleashing their potential functionalities for countless applications in industrial biotechnology. This review provides an overview of enzyme immobilization techniques and 3D printing technologies, followed by illustrations of the latest 3D printed enzyme-immobilized industrial and clinical applications. The unique advantages of harnessing 3D printing as an enzyme immobilization technique will be presented, alongside a discussion on its potential limitations. Finally, the future perspectives of integrating 3D printing with enzyme immobilization will be considered, highlighting the endless possibilities that are achievable in both research and industry

Photostability of poly(phenylacetylene) (PPA) derivatives is closely linked to the dynamic helical behavior of the polyene scaffold. Quasi-static PPAs are stable under light exposure, while a photochemical electrocyclization is produced in dynamic PPAs. Helical polymers such as poly(phenylacetylene)s (PPAs) are interesting materials due to the possibility of tuning their helical scaffold (sense and elongation) once they have been prepared and by the presence of external stimuli. The main limitation in the application of PPAs is their poor photostability. These polymers degrade under visible light exposure through a photochemical electrocyclization process. In this work, it was demonstrated, through a selected example, how the photochemical degradation in PPAs is directly related to their dynamic helical behavior. Thus, while PPAs with dynamic helical structures show poor photostability under UV/Vis light exposure, poly-(R)-1, bearing an enantiopure sulfoxide group as pendant group and designed to have a quasi-static helical behavior, shows a large photostability due to the restricted conformational composition at the polyene backbone, needed to orient the conjugated double bonds prior to the photochemical electrocyclization process and the subsequent degradation of the material

Unisexual bryophytes provide excellent models to study the mechanisms that regulate the frequency of sexual versus asexual reproduction in plants, and their ecological and evolutionary implications. Here, we determined sex expression, phenotypic sex ratio, and individual shoot traits in 242 populations of the cosmopolitan moss Pseudoscleropodium purum spanning its whole distributional range. We tested whether niche differentiation, sex-specific differences in shoot size, and biogeographical history explained the spatial variation of reproductive traits. We observed high levels of sex expression and predominantly female-biased populations, although both traits showed high intraspecific variation among populations. Sex expression and sex ratio were partly explained by current macroscale environmental variation, with male shoots being less frequent at the higher end of the environmental gradients defined by the current distribution of the species. Female bias in population sex ratio was significantly lower in areas recolonized after the last glacial maximum (recent populations) than in glacial refugia (long-term persistent populations). We demonstrated that reproductive trait variation in perennial unisexual mosses is partially driven by macroscale and historical environmental variation. Based on our results, we hypothesize that sexual dimorphism in environmental tolerance and vegetative growth contribute to sex ratio bias over time, constraining the chances of sexual reproduction, especially in long-term persistent populations. Further studies combining genetic analyses and population monitoring should improve our understanding of the implications of the intraspecific variation in the frequency of sexual versus asexual reproduction in bryophyte population fitness and eco-evolutionary dynamics

Low atomicity clusters present properties dependent on the size, due to the quantum confinement, with well-defined electronic structures and high stability. Here it is shown that Ag5 clusters catalyze the complete oxidation of sulfur to S+6. Ag5 catalytic activity increases with different oxidant species in the order O2 ≪ H2O2 < OH•. Selective oxidation of thiols on the cysteine residues of glutathione and thioredoxin is the primary mechanism human cells have to maintain redox homeostasis. Contingent upon oxidant concentration, Ag5 catalyzes the irreversible oxidation of glutathione and thioredoxin, triggering apoptosis. Modification of the intracellular environment to a more oxidized state to mimic conditions within cancer cells through the expression of an activated oncogene (HRASG12V) or through ARID1A mutation, sensitizes cells to Ag5 mediated apoptosis. While cancers evolve to evade treatments designed to target pathways or genetic mutations that drive them, they cannot evade a treatment that takes advantage of aberrant redox homeostasis, which is essential for tumor progression and metastasis. Ag5 has antitumor activity in mice with orthotopic lung tumors reducing primary tumor size, and the burden of affected lymphatic nodes. The findings suggest the unique intracellular redox chemistry of Ag5 may lead to new redox-based approaches to cancer therapy