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José Miguel Senabre-Gallego,1 Carlos Santos-Ramirez,2 Gregorio Santos-Soler,1 Esteban Salas-Heredia,1 Mabel Sánchez-Barrioluengo,3 Xavier Barber,4 José Rosas1 On behalf of the AIRE-MB group 1Rheumatology, Hospital Marina Baixa, Villajoyosa, 2Rheumatology, Hospital Marina Salud, Denia, 3INGENIO (Instituto de Gestión de la Inovación y del Conocimiento) (CSIC [Consejo Superior de Investigaciones Científicas]-UPV [Universidad Politécnica de Valencia]), Universitat Politècnica de València, Valencia, 4CIO (Centro de Investigación Operativa)-UMH (Universidad Miguel Hernández), Universidad Miguel Henández, Elche, Spain Abstract: To date, anti-tumor necrosis factor alfa (anti-TNF-α) therapy is the only alternative to nonsteroidal anti-inflammatory drugs for the treatment of ankylosing spondylitis. Etanercept is a soluble TNF receptor, with a mode of action and pharmacokinetics different to those of antibodies and distinctive efficacy and safety. Etanercept has demonstrated efficacy in the treatment of ankylosing spondylitis, with or without radiographic sacroiliitis, and other manifestations of the disease, including peripheral arthritis, enthesitis, and psoriasis. Etanercept is not efficacious in inflammatory bowel disease, and its efficacy in the treatment of uveitis appears to be lower than that of other anti-TNF drugs. Studies of etanercept confirmed regression of bone edema on magnetic resonance imaging of the spine and sacroiliac joint, but failed to reduce radiographic progression, as do the other anti-TNF drugs. It seems that a proportion of patients remain in disease remission when the etanercept dose is reduced or administration intervals are extended. Etanercept is generally well tolerated with an acceptable safety profile in the treatment of ankylosing spondylitis. The most common adverse effect of etanercept treatment is injection site reactions, which are generally self-limiting. Reactivation of tuberculosis, reactivation of hepatitis B virus infection, congestive heart failure, demyelinating neurologic disorders, hematologic disorders like aplastic anemia and pancytopenia, vasculitis, immunogenicity, and exacerbation or induction of psoriasis are class effects of all the anti-TNF drugs, and have been seen in patients with ankylosing spondylitis. However, etanercept is less likely to induce reactivation of tuberculosis than the other anti-TNF drugs and it has been suggested that etanercept might be less immunogenic, especially in ankylosing spondylitis. Acute uveitis, Crohn’s disease, and sarcoidosis are other adverse events that have been rarely associated with etanercept therapy in patients with ankylosing spondylitis. Keywords: ankylosing spondylitis, etanercept, spondyloarthritis, efficacy, safety

Background: Bosentan, an oral dual endothelin receptor antagonist, has shown to be effective in the treatment of pulmonary arterial hypertension (PAH) and ischaemic digital ulcers (IDU) in systemic sclerosis (SSc) patients. Some clinical reports also suggest a short-term benefit in treating Raynaud's phenomenon and cutaneous fibrosis (CF) in SSc patients. The aim of this case series was to describe the long-term benefit of bosentan in treating CF.Methods: In an open, non-controlled prospective case series, SSc patients were treated with bosentan (mean follow-up: 11 +/- 6.4 months) on standard doses. CF was assessed with the modified Rodnan Skin Score (mRSS).Results: Six patients had limited SSc (LSSc) and seven diffuse SSc (DSSc). Overall, 92% were women, mean age was 51 +/- 17 years and mean SSc duration was 12 +/- 7.7 years. Indications for treatment were SSc associated PAH (five patients) and unresponsive IDU (eight patients). All SSc patients experienced amelioration of CF, with a mean mRSS reduction of 46% (p = 0.001), 45.7% (p = 0.018) and 46.5% (p = 0.026) for the whole group, DSSc and LSSc, respectively. Improvement of skin was independent of the duration of SSc, baseline skin score and type of SSc. Generally, bosentan treatment was well tolerated. Three patients (23%) had an elevation of liver transaminases > 3 times above the upper limit of normal, including an acute symptomatic cholestatic hepatitis which led to patient's withdrawal.Conclusions: This case series indicates that bosentan can improve CF in SSc and that improvement is maintained in the long-term. Given the lack of effective therapies for SSc cutaneous involvement, larger studies should be addressed at confirming this benefit and an earlier use of this drug should be considered in these patients. Since bosentan has various beneficial effects in SSc it should be considered as a central therapeutic strategy in these patients. [ABSTRACT FROM AUTHOR]

The design of novel low-dimensional carbon materials is at the forefront of modern chemistry. Recently, on-surface covalent synthesis has emerged as a powerful strategy to synthesize previously precluded compounds and polymers. Here, we report a scanning probe microscopy study, complemented by theoretical calculations, about the sequential skeletal rearrangement of sumanene-based precursors into a coronene-based organometallic network by stepwise intra- and inter-molecular reactions on Au(111). Interestingly, upon higher annealing, the formed organometallic networks evolve into two-dimensional coronene-based covalently-linked patches through intermolecular homocoupling reactions. A new reaction mechanism is proposed based on the role of C-Au-C motifs to promote two stepwise carbon-carbon couplings to form cyclobutadiene bridges. Our results pave avenues for the conversion of molecular precursors on surfaces, affording the design of unexplored two-dimensional organometallic and covalent materials., (© 2024 Wiley‐VCH GmbH.)

We finely designed a set of [2]rotaxanes with urea threads and tested them as hydrogen-bonding phase-transfer catalysts in two different nucleophilic substitutions requiring the activation of the reactant fluoride anion. The [2]rotaxane bearing a fluorinated macrocycle and a fluorine-containing urea thread displayed significantly enhanced catalytic activity in comparison with the combination of both noninterlocked components. This fact highlights the notably beneficial role of the mechanical bond, cooperatively activating the processes through hydrogen-bonding interactions.

Background: Despite progress made by many countries on the adoption of plain tobacco packaging laws over the last years, low- and middle-income countries, with a large supply of loose cigarettes via informal vendors, remain far behind., Aim: To study the potential effectiveness of plain tobacco packaging and dissuasive cigarette sticks, via willingness-to-pay estimates, when illicit cigarette options are available., Methods: We conducted a discrete choice experiment (DCE) in which respondents chose licit and illicit products with three attributes: packaging (standard vs. plain packaging), stick design (branded stick vs. stick with warning), and price level. The sample, collected on 12/2021, consisted of 1761 respondents from an internet panel involving smokers and nonsmokers. Conditional logit and latent class models were used to estimate the willingness-to-pay (WTP) to avoid restrictive packaging elements., Results: Nonsmokers are willing to pay USD $5.63 for a pack of cigarettes to avoid plain packaging, which is higher than the actual commercial price of illicit cigarettes (USD $2.40). The WTP increases to USD $12.14 in the presence of illicit alternatives. Smokers are also willing to pay to avoid illicit options, which they also deem riskier, and the presence of such options increases the WTP to avoid plain packaging. However, nonsmokers do not perceive the illicit option as riskier. The dissuasive stick (stick with warning) does not affect perceptions of risk and plays a small role in terms of choice for both smokers and nonsmokers., Conclusions: Even in the presence of illicit tobacco alternatives, plain packaging seems to be as effective in reducing the attractiveness of tobacco products in Colombia as in other countries that have already adopted it. Given conflicting results on the case for dissuasive sticks, there is a need for more research., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Objective: 1) To evaluate the ability of baseline and on 24 h serum calprotectin, in comparison to canonical biomarkers (lactate and procalcitonin), for prognosis of 28-day mortality in critically ill septic patients; and 2) To develop a predictive model combining the three biomarkers., Design: A single-center, retrospective study., Setting: Intensive Care Unit of a university hospital., Patients or Participants: One hundred and seventy three septic pacientes were included., Interventions: Measurement of baseline lactate, procalcitonin and calprotectin level and procalcitonin and calprotectin levels on 24 h., Main Variables of Interest: Demographics and comorbidities, SOFA score on ICU admission, baseline lactate, procalcitonin and calprotectin on admission and on 24 h and 28-day mortality., Results: 1) On ICU admission, lactate was the only biomarker achieving a significant accuracy (AUC: 0.698); 2) On 24 h, no differences were found on procalcitonin and calprotectin levels. Procalcitonin and calprotectin clearances were significantly lower in non-survivors and both achieved a moderate performance (AUCs: 0.668 and 0.664, respectively); 3) A biomarker based-model achieved a significant accuracy (AUC: 0.766), trending to increase (AUC: 0.829) to SOFA score alone; y 4) Baseline lactate levels and procalcitonin and calprotectin clearance were independent predictors for the outcome., Conclusions: 1) Baseline and on 24 h calprotectina and procalcitonin levels lacked ability in predicting 28-day mortality; 2) Accuracy of clearance of both biomarkers was moderate; and 3) Combination of SOFA score and the predictive biomarker based-model showed a high prognostic accuracy., (Copyright © 2024 Elsevier España, S.L.U. and SEMICYUC. All rights reserved.)

The synthesis of lanthanide-based organometallic sandwich compounds is very appealing regarding their potential for single-molecule magnetism. Here, it is exploited by on-surface synthesis to design unprecedented lanthanide-directed organometallic sandwich complexes on Au(111). The reported compounds consist of Dy or Er atoms sandwiched between partially deprotonated hexahydroxybenzene molecules, thus introducing a distinct family of homoleptic organometallic sandwiches based on six-membered ring ligands. Their structural, electronic, and magnetic properties are investigated by scanning tunneling microscopy and spectroscopy, X-ray absorption spectroscopy, X-ray linear and circular magnetic dichroism, and X-ray photoelectron spectroscopy, complemented by density functional theory-based calculations. Both lanthanide complexes self-assemble in close-packed islands featuring a hexagonal lattice. It is unveiled that, despite exhibiting analogous self-assembly, the erbium-based species is magnetically isotropic, whereas the dysprosium-based compound features an in-plane magnetization., (© 2024 The Authors. Advanced Science published by Wiley‐VCH GmbH.)

In recent decades, policy initiatives involving increases in the tobacco tax have increased pressure on budget allocations in poor households. In this study, we examine this issue in the context of the expansion of the social welfare state that has taken place over the last two decades in several emerging economies. This study explores the case of Colombia between 1997 and 2011. In this period, the budget share of the poorest expenditure quintile devoted to tobacco products of smokers' households doubled. We analyse the differences between the poorest and richest quintiles concerning the changes in budget shares, fixing a reference population over time to avoid demographic composition confounders. We find no evidence of crowding-out of education or healthcare expenditures. This is likely to be the result of free universal access to health insurance and basic education for the poor. For higher-income households, tobacco crowds out expenditures on entertainment, leisure activities, and luxury expenditures. This finding should reassure policymakers who are keen to impose tobacco taxes as an element of their public health policy., Competing Interests: The authors have declared that no competing interests exist., (Copyright: © 2024 Gallego et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

Antiferromagnetic spintronics is a rapidly emerging field with the potential to revolutionize the way information is stored and processed. One of the key challenges in this field is the development of novel 2D antiferromagnetic materials. In this paper, the first on-surface synthesis of a Co-directed metal-organic network is reported in which the Co atoms are strongly antiferromagnetically coupled, while featuring a perpendicular magnetic anisotropy. This material is a promising candidate for future antiferromagnetic spintronic devices, as it combines the advantages of 2D and metal-organic chemistry with strong antiferromagnetic order and perpendicular magnetic anisotropy., (© 2023 The Authors. Small published by Wiley‐VCH GmbH.)

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 A a-a embeds two azulene units formed through oxidative ring-closure of methyl substituents, while A a-s contains one azulene unit and one Stone-Wales defect, formed by the combination of oxidative ring-closure and skeletal ring-rearrangement reactions. A a-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 (B a-a , B a-s , B s-a and B s-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., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Fullertubes, that is, fullerenes consisting of a carbon nanotube moiety capped by hemifullerene ends, are emerging carbon nanomaterials whose properties show both fullerene and carbon nanotube (CNT) traits. Albeit it may be expected that their electronic states show a certain resemblance to those of the extended nanotube, such a correlation has not yet been found or described. Here it shows a scanning tunneling microscopy (STM) and spectroscopy (STS) characterization of the adsorption, self-assembly, and electronic structure of 2D arrays of [5,5]-C 90 fullertube molecules on two different noble metal surfaces, Ag(111) and Au(111). The results demonstrate that the shape of the molecular orbitals of the adsorbed fullertubes corresponds closely to those expected for isolated species on the grounds of density functional theory calculations. Moreover, a comparison between the electronic density profiles in the bands of the extended [5,5]-CNT and in the molecules reveals that some of the frontier orbitals of the fullertube molecules can be described as the result of the quantum confinement imposed by the hemifullerene caps to the delocalized band states in the extended CNT. The results thus provide a conceptual framework for the rational design of custom fullertube molecules and can potentially become a cornerstone in the understanding of these new carbon nanoforms., (© 2023 The Authors. Small published by Wiley-VCH GmbH.)

Immune checkpoint inhibitors targeting the programmed cell death protein 1 (PD-1) pathway have revolutionized cancer immunotherapy by enhancing the immune system's ability to combat cancer cells. However, this innovative approach comes with a distinctive set of challenges, as these therapies can lead to immune-related adverse events (irAEs) due to their mechanism of action. The most common irAEs involve the skin, gastrointestinal tract, liver, endocrine system, and lungs. These events can range from mild skin rashes to severe colitis, pneumonitis, or even autoimmune organ damage. These adverse effects usually appear with an average of 5-15 weeks from the start of treatment depending on the affected organ. This article presents a case report of a delayed related-mediated hepatitis, after 24 months of treatment with pembrolizumab and almost 3 months after its termination, and a review of the scientific literature on cases of delayed immune-related hepatitis caused by anti-PD1. This case highlights the importance of monitoring patients treated with immune checkpoint inhibitors after cessation as a growing number of patients stop treatment due to achieving durable responses., (Copyright © 2023 Wolters Kluwer Health, Inc. All rights reserved.)

Introduction: Psoriatic arthritis (PsA) is a complex and heterogeneous inflammatory disease. Secukinumab, a biologic disease-modifying antirheumatic drug (bDMARD), has extensive clinical evidence of efficacy and safety in the treatment of PsA but data in clinical practice are still limited. This study aims to provide real-world evidence on secukinumab use, effectiveness, and persistence in PsA., Methods: A retrospective, multicenter study was conducted on patients diagnosed with PsA and treated with secukinumab up to June 2021 at 12 centers in the Valencian Community (Spain). Data on DAS28-CRP, DAPSA, Tender and Swollen Joint Counts (TJC, SJC), enthesitis, dactylitis, skin and nail involvement, pain, patient and physician global assessment (ptGA, phGA) using 100-mm visual analog scale (VAS), and persistence for up to 24 months were collected., Results: A total of 178 patients were included (49% men; mean [standard deviation, SD] age: 51.4 [10.5] years; 39% obese). Secukinumab was used as a first-, second-, or ≥ third-line bDMARD in 37, 21, and 42% of patients, respectively. The percentage of patients achieving at least low disease activity (DAS28-CRP ≤ 3.2) increased from 25% at baseline to 66% at month 6 (M6) and was maintained (75%) up to M24. Mean (SD) DAS28-CRP baseline values (3.9 [1.2]) decreased to 2.9 (1.1) ( p  < 0.001) at M6 and remained low through M24 (2.6 [1.1]) ( p  < 0.001). Secukinumab also improved peripheral arthritis increasing the percentage of patients with TJC = 0 (20% baseline; 57% M24) and SJC = 0 (37% baseline; 80% M24). Treatment reduced the percentage of patients with enthesitis (25% baseline; 6% M24), dactylitis (20% baseline; 4% M24), and skin (70% baseline; 17% M24), and nail (32% baseline; 2% M24) involvement. Additionally, we observed improvements in the mean pain VAS (-26.4 mm M24), ptGA (-26.2 mm M24), and phGA (-24.8 mm M24). Secukinumab showed an overall 24-month persistence rate of 67% (95% confidence interval [CI]: 60-74%). Patients receiving first-line secukinumab showed the highest 24-month persistence rate (83, 95% CI: 73-92; p  = 0.024)., Conclusion: Secukinumab showed long-term effectiveness across the six key PsA domains thus reducing disease activity and pain, which are major treatment goals. This was accompanied by high persistence rates, especially in bDMARD naive patients., Competing Interests: FS received honoraria as a consultant from AbbVie, Pfizer, Astra Zeneca, and UCB. Grant/Research support from: AbbVie, Novartis, Eli Lilly, Roche, and BMS. JS-G reports personal fees and non-financial support from Abbvie, non-financial support from BMS, personal fees from Celgene, personal fees from Janssen, non-financial support from Lilly, non-financial support from MSD, personal fees from Novartis, non-financial support from Pfizer, non-financial support from Roche, and non-financial support from UCB, outside the submitted work. The remaining authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest. The authors declare that this study received funding from Novartis Farmacéutica, S.A. The funder had the following involvement in the study: study design, interpretation of data, the writing of this article, and the decision to submit it for publication. The author(s) declared that they were an editorial board member of Frontiers, at the time of submission. This had no impact on the peer review process and the final decision., (Copyright © 2023 Alegre-Sancho, Núñez-Monje, Campos-Fernández, Balaguer-Trull, Robustillo-Villarino, Aguilar-Zamora, Garijo-Bufort, Pedraz-Penalva, Peña-González, de la Morena, Bedoya-Sanchís, Yankova-Komsalova, Conesa-Mateos, Martinez-Cristóbal, Navarro-Blasco, Senabre-Gallego and Sivera.)

The synthesis of two-dimensional metal-organic networks (2D-MOCNs) on solid substrates is a rapidly growing field of research due to their potential applications in gas sensing, catalysis, energy storage, spintronics, and quantum information. In addition, the possibility of using lanthanides as coordination nodes makes them a very straightforward alternative to create an ordered array of magnetic atoms on a surface, thus paving the way for their use in information storage at the single-atom level. This feature article reviews the strategies to design two-dimensional periodic nanoarchitectures comprising lanthanide atoms in ultra-high vacuum (UHV) environment, focusing on lanthanide-directed 2D-MOCNs on metal surfaces and decoupling substrates. The characterization of their structure, electronic, and magnetic properties is also discussed, including the use of state-of-the-art scanning probe microscopies and photoelectron spectroscopies, complemented by density functional theory calculations and multiplet simulations.

The design of a well-ordered arrangement of atoms on a solid surface has long been sought due to the envisioned applications in many different fields. On-surface synthesis of metal-organic networks is one of the most promising fabrication techniques. Hierarchical growth, which involves coordinative schemes with weaker interactions, favours the formation of extended areas with the desired complex structure. However, the control of such hierarchical growth is in its infancy, particularly for lanthanide-based architectures. Here the hierarchical growth of a Dy-based supramolecular nanoarchitecture on Au(111) is described. Such an assembly is based on a first hierarchical level of metallo-supramolecular motifs, which in a second level of hierarchy self-assemble through directional hydrogen bonds, giving rise to a periodic two-dimensional supramolecular porous network. Notably, the size of the metal-organic based tecton of the first level of hierarchy can be tailored by modifying the metal-ligand stoichiometric ratio., (© 2023 Wiley-VCH GmbH.)

Background: Secukinumab is a biologic disease-modifying antirheumatic drug (bDMARD) that has demonstrated efficacy in the treatment of axial spondyloarthritis (axSpA, i.e., ankylosing spondylitis and non-radiographic axSpA) across various clinical trials. However, data of secukinumab in clinical practice is still limited. Here, we aimed to provide real-world data on secukinumab use, effectiveness, and persistence in axSpA., Patients and Methods: Retrospective, multicenter study of patients with a diagnosis of axSpA treated with secukinumab at 12 centers up to June 2021 in the Valencian Community (Spain). Information was gathered on BASDAI measurement, pain, patient and physician global assessment (ptGA, phGA) using a 100-mm visual analog scale (VAS), persistence and other secondary variables by treatment line (first, second, and ≥ third) for up to 24 months., Results: 221 patients were included (69% men; mean age [standard deviation, SD]: 46.7 [12.1] years old). Secukinumab was used as a first-line bDMARD in 38% of patients, as a second-line in 34% and as a ≥ hird-line in 28%. The percentage of patients achieving low disease activity (BASDAI<4) increased from 9% at baseline to 48% at month 6 and was maintained (49%) up to month 24. The greatest improvement in BASDAI was observed in naïve patients (month 6: -2.6; month 24: -3.7), followed by second-line (month 6: -1.9; month 24: -3.1) and ≥ third-line (month 6: -1.3; month 24: -2.3) patients. Reductions in mean pain VAS (-23.3; -31.9), ptGA (-25.1; -31.9) and phGA (-25.1; -31) were also observed at 6 and 24 months. Secukinumab showed an overall 12-months persistence rate of 70% (95% confidence interval [CI]: 63-77%) and a 24-months persistence rate of 58% (95% CI, 51-66%). Patients receiving first-line secukinumab had the highest 24-months persistence rate ( p  = 0.05)., Conclusion: Secukinumab improved disease activity in axSpA patients, especially in naive, and second-line patients, which was accompanied by high persistence rates up to 24 months., Competing Interests: FS received honoraria as a consultant from AbbVie, Pfizer, Astra Zeneca. Grant/Research support from AbbVie, Novartis, Eli Lilly, Roche, BMS. JMSG reports personal fees and non-financial support from Abbvie, non-financial support from BMS, personal fees from Celgene, personal fees from Janssen, non-financial support from Lilly, non-financial support from MSD, personal fees from Novartis, non-financial support from Pfizer, non-financial support from Roche, non-financial support from UCB, outside the submitted work. The remaining authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 Sivera, Núñez-Monje, Campos-Fernández, Balaguer-Trull, Robustillo-Villarino, Aguilar-Zamora, Garijo-Bufort, López-Gómez, Peña-González, de la Morena, Bedoya-Sanchís, Yankova-Komsalova, Conesa-Mateos, Martínez-Cristóbal, Navarro-Blasco, Senabre-Gallego and Alegre-Sancho.)

The coordination of lanthanides atoms in two-dimensional surface-confined metal-organic networks is a promising path to achieve an ordered array of single atom magnets. These networks are highly versatile with plenty of combinations of molecular linkers and metallic atoms. Notably, with an appropriate choice of molecules and lanthanide atoms it should be feasible to tailor the orientation and intensity of the magnetic anisotropy. However, up to now only tilted and almost in-plane easy axis of magnetizations were reported in lanthanide-based architectures. Here we introduce an Er-directed two-dimensional metallosupramolecular network on Cu(111) featuring strong out-of-plane magnetic anisotropy. Our results will contribute to pave avenues for the use of lanthanides in potential applications in nanomagnetism and spintronics.

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.

The effectiveness of command-and-control policies related to tobacco use has been studied in high-income countries. Still, there is limited evidence of their effects in low and middle-income countries. We explore the case of Colombia, a country that introduced a business-supported smoking ban in bars and restaurants and all public indoor spaces in 2010. This paper investigates the effect of smoking bans in bars and restaurants on smoking prevalence in Bogotá, Colombia. In this paper, we use the matching with triple-differences technique in analyzing household consumption data from the 2007 and 2011 quality of life surveys. This is done by exploiting their geographical proximity and variation in the density of commercial areas. We found that after the smoking ban implementation, smoking prevalence reduced in households near high-density commercial blocks compared to households near low-density commercial blocks (-10.8 pp.). The impact is larger for households with children and older household heads. Since households near high-density commercial blocks are more frequently exposed to smoking than households near low-density commercial blocks, the former would be more willing to internalize the smoking de-normalization process., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

Purpose: To investigate the quantity and quality of sleep hours in young athletes in a professional football club, to study if there is a significant relationship with mood state and subjective well-being, and to identify the relationship between sleep and quarterly academic performance. We also explored the relationship between sleep and quarterly academic performance., Method: the study included 261 players of the various age group categories from football at Barcelona Football Club (average age:13.04 ± 3.16). Participants maintained a sleep diary and completed questionnaires on their mood state and the quantity and quality of their sleep., Results: 70% of the athletes slept less hours than recommended by the American National Sleep Foundation. Athletes with worse quantity and quality of sleep showed negative effects on academic results., Conclusions: The results show that the majority of young players sleep less than recommended and show that those who sleep more hours obtain better academic results.

The design of antiferromagnetic nanomaterials preserving large orbital magnetic moments is important to protect their functionalities against magnetic perturbations. Here, we exploit an archetype H 6 HOTP species for conductive metal-organic frameworks to design a Co-HOTP one-atom-thick metal-organic architecture on a Au(111) surface. Our multidisciplinary scanning probe microscopy, X-ray absorption spectroscopy, X-ray linear dichroism, and X-ray magnetic circular dichroism study, combined with density functional theory simulations, reveals the formation of a unique network design based on threefold Co +2 coordination with deprotonated ligands, which displays a large orbital magnetic moment with an orbital to effective spin moment ratio of 0.8, an in-plane easy axis of magnetization, and large magnetic anisotropy. Our simulations suggest an antiferromagnetic ground state, which is compatible with the experimental findings. Such a Co-HOTP metal-organic network exemplifies how on-surface chemistry can enable the design of field-robust antiferromagnetic materials.

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.

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 (:CBr 2 ) 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., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

The synthesis of long n-peri-acenes (n-PAs) is challenging as a result of their inherent open-shell radical character, which arises from the presence of parallel zigzag edges beyond a certain n value. They are considered as π-electron model systems to study magnetism in graphene nanostructures; being potential candidates in the fabrication of optoelectronic and spintronic devices. Here, we report the on-surface formation of the largest pristine member of the n-PA family, i.e. peri-heptacene (n=7, 7-PA), obtained on an Au(111) substrate under ultra-high vacuum conditions. Our high-resolution scanning tunneling microscopy investigations, complemented by theoretical simulations, provide insight into the chemical structure of this previously elusive compound. In addition, scanning tunneling spectroscopy reveals the antiferromagnetic open-shell singlet ground state of 7-PA, exhibiting singlet-triplet spin-flip inelastic excitations with an effective exchange coupling (J eff ) of 49 meV., (© 2022 Wiley-VCH GmbH.)

The design of lanthanide multinuclear networks is an emerging field of research due to the potential of such materials for nanomagnetism, spintronics, and quantum information. Therefore, controlling their electronic and magnetic properties is of paramount importance to tailor the envisioned functionalities. In this work, a multidisciplinary study is presented combining scanning tunneling microscopy, scanning tunneling spectroscopy, X-ray absorption spectroscopy, X-ray linear dichroism, X-ray magnetic circular dichroism, density functional theory, and multiplet calculations, about the supramolecular assembly, electronic and magnetic properties of periodic dinuclear 2D networks based on lanthanide-pyridyl interactions on Au(111). Er- and Dy-directed assemblies feature identical structural architectures stabilized by metal-organic coordination. Notably, despite exhibiting the same +3 oxidation state, there is a shift of the energy level alignment of the unoccupied molecular orbitals between Er- and Dy-directed networks. In addition, there is a reorientation of the easy axis of magnetization and an increment of the magnetic anisotropy when the metallic center is changed from Er to Dy. Thus, the results show that it is feasible to tune the energy level alignment and magnetic anisotropy of a lanthanide-based metal-organic architecture by metal exchange, while preserving the network design., (© 2022 The Authors. Small published by Wiley-VCH GmbH.)

Background: Since 1993, Colombia has had a mandatory social health insurance scheme that aims to provide universal health coverage to all citizens. However, some contributory regime participants purchase voluntary private health insurance (VPHI) to access better quality health services (i. e., physicians and hospitals), shorter waiting times, and a more extensive providers' network. This article aims to estimate the price elasticity of demand for the VPHI market in Colombia., Methods: We use data from the 2016-2017 consumer expenditure national survey and apply a Heckman selection model to address the selection problem into purchasing private insurance. Using the estimation results to further estimate the price semi-elasticity for VPHI, we then calculate the price elasticity for the households' health expenditure and acquisition of VHPI., Results: Our main findings indicate that a 1% VPHI price increase reduces the proportion of households affiliated to a VPHI in the country by about 2.32% to 4.66%, with robust results across sample restrictions. There are relevant differences across age groups, with younger households' heads being less responsive to VPHI price changes., Conclusions: We conclude that the VPHI demand in Colombia is noticeably elastic, and therefore tax policy changes can have a significant impact on public health insurance expenditures. The government should estimate the optimal VPHI purchase in order to reduce any welfare loss that the current arrangement might be generating., (© 2022. The Author(s).)

First-row transition metal oxides are promising materials for catalyzing the oxygen evolution reaction. Surface sensitive techniques provide a unique perspective allowing the study of the structure, adsorption sites, and reactivity of catalysts at the atomic scale, which furnishes rationalization and improves the design of highly efficient catalytic materials. Here, a scanning probe microscopy study complemented by density functional theory on the structural and electronic properties of CoO nanoislands grown on Au(111) is reported. Two distinct phases are observed: The most extended displays a Moiré pattern (α-region), while the less abundant is 1Co:1Au coincidental (β-region). As a result of the surface registry, in the β-region the oxide adlayer is compressed by 9%, increasing the unoccupied local density of states and enhancing the selective water adsorption at low temperature through a cobalt inversion mechanism. Tip-induced voltage pulses irreversibly transform α- into β-regions, thus opening avenues to modify the structure and reactivity of transition metal oxides by external stimuli like electric fields., (© 2022 Wiley-VCH GmbH.)

The synthesis of nanographenes (NGs) with open-shell ground states have recently attained increasing attention in view of their interesting physicochemical properties and great prospects in manifold applications as suitable materials within the rising field of carbon-based magnetism. A potential route to induce magnetism in NGs is the introduction of structural defects, for instance non-benzenoid rings, in their honeycomb lattice. Here, we report the on-surface synthesis of three open-shell non-benzenoid NGs ( A 1 , A 2 and A 3 ) on the Au(111) surface. A 1 and A 2 contain two five- and one seven-membered rings within their benzenoid backbone, while A 3 incorporates one five-membered ring. Their structures and electronic properties have been investigated by means of scanning tunneling microscopy, noncontact atomic force microscopy and scanning tunneling spectroscopy complemented with theoretical calculations. Our results provide access to open-shell NGs with a combination of non-benzenoid topologies previously precluded by conventional synthetic procedures.

The atomically precise control over the size, shape and structure of nanographenes (NGs) or the introduction of heteroatom dopants into their sp 2 -carbon lattice confer them valuable electronic, optical and magnetic properties. Herein, we report on the design and synthesis of a hexabenzocoronene derivative embedded with graphitic nitrogen in its honeycomb lattice, achieved via on-surface assisted cyclodehydrogenation on the Au(111) surface. Combined scanning tunnelling microscopy/spectroscopy and non-contact atomic force microscopy investigations unveil the chemical and electronic structures of the obtained dicationic NG. Kelvin probe force microscopy measurements reveal a considerable variation of the local contact potential difference toward lower values with respect to the gold surface, indicative of its positive net charge. Altogether, we introduce the concept of cationic nitrogen doping of NGs on surfaces, opening new avenues for the design of novel carbon nanostructures., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)