Pairing and unpairing electron densities in organic systems: Two-electron three center through space and through bonds interactions

Two-electron three-center bonding interactions in organic ions like methonium (CH + 5 ), ethonium (C2H + 7 ), and protonated alkanes n−C4H + 11 isomers (butonium cations) are described and characterized within the theoretical framework of the topological analysis of the electron density decomposition into its effectively paired and unpaired contributions. These interactions manifest in some of this type of systems as a concentration of unpaired electron cloud around the bond paths, in contrast to the well known paradigmatic boron hydrids in which it is not only concentrated close to the atomic nucleus and the bond paths but out of them and over the region defined by the involved atoms as a whole. This result permits to propose an attempt of classification for these interactions based in such manifestations. In the first type, it is called as interactions through bonds and in the second type as interactions through space type.Fil: Lobayan, Rosana Maria. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas y Naturales y Agrimensura. Departamento de Física; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Bochicchio, Roberto Carlos. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Física de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Física de Buenos Aires; Argentin

Right-Wing Authoritarianism and Antipathy Toward Immigrants and Sexual Minorities in the Early Days of the Coronavirus Pandemic in Italy

Theory and research in social, evolutionary, and political psychology indicates that subjective feelings of threat and exposure to objectively threatening circumstances—including pandemic diseases—may contribute to increased affinities for political conservatism, right-wing authoritarianism, and prejudice against out-group members. We investigated these possibilities in the context of Italy, which was the first Western country to be severely affected by the spread of COVID-19. Early on in the pandemic, from March 3–8, 2020, we surveyed 757 Italian adults ranging in age from 18 to 78 years. Results revealed that antipathy toward immigrants and sexual minorities was predicted by (male) sex, COVID-19 anxiety, RWA, and political distrust. Furthermore, COVID-19 anxiety magnified the effect of RWA on disliking of immigrants and sexual minorities (but not obese or disabled people). Contrary to prediction, political trust failed to attenuate the effects of COVID-19 anxiety or RWA on out-group antipathy. Implications for the theories of right-wing authoritarianism and political ideology as motivated social cognition, as well as the state of contemporary Italian politics are discussed

The Role of Internalized Transphobia, Loneliness, and Social Support in the Psychological Well-Being of a Group of Italian Transgender and Gender Non-Conforming Youths

Although transgender and gender non-conforming (TGNC) youth represent a highly resilient community capable of successfully overcoming adverse life circumstances, they still face social stigma that negatively impacts their health, being at risk of developing negative feelings toward their own TGNC identity (i.e., internalized transphobia). A poorly investigated dimension in TGNC health research is perceived loneliness. Thus, within the minority stress theory, the present study aimed to investigate the mediating role of loneliness and the moderating role of social support in the relationship between internalized transphobia and psychological well-being among 79 Italian TGNC youths aged 18 to 30-years-old who participated in an online survey. The main results show that loneliness partially mediated the relationship between internalized transphobia and psychological well-being. In addition, social support emerged as a significant moderator, as the impact of internalized transphobia on psychological well-being decreased at moderate and high levels of social support, but not at low levels. The findings have significant implications for clinical practice and psychosocial interventions to reduce the impact of internalized stigma and stress on psychological healt

The Role of Internalized Transphobia, Loneliness, and Social Support in the Psychological Well-Being of a Group of Italian Transgender and Gender Non-Conforming Youths

lthough transgender and gender non-conforming (TGNC) youth represent a highly resilient community capable of successfully overcoming adverse life circumstances, they still face social stigma that negatively impacts their health, being at risk of developing negative feelings toward their own TGNC identity (i.e., internalized transphobia). A poorly investigated dimension in TGNC health research is perceived loneliness. Thus, within the minority stress theory, the present study aimed to investigate the mediating role of loneliness and the moderating role of social support in the relationship between internalized transphobia and psychological well-being among 79 Italian TGNC youths aged 18 to 30-years-old who participated in an online survey. The main results show that loneliness partially mediated the relationship between internalized transphobia and psychological well-being. In addition, social support emerged as a significant moderator, as the impact of internalized transphobia on psychological well-being decreased at moderate and high levels of social support, but not at low levels. The findings have significant implications for clinical practice and psychosocial interventions to reduce the impact of internalized stigma and stress on psychological health

Negative Affectivity, Authoritarianism, and Anxiety of Infection Explain Early Maladjusted Behavior During the COVID-19 Outbreak

During the first phase of the COVID-19 outbreak, Italy experienced problems of public order and maladjusted behavior. This study assessed the role of negative affectivity, right-wing authoritarianism, and anxiety of COVID-19 infection in explaining a variety of the maladjusted behaviors (i.e., “China-phobic” discrimination, panic buying) observed with an Italian sample. Specifically, we examined the effect of Negative Affectivity and Right-Wing Authoritarianism on maladjusted behaviors, and the moderating role of anxiety of infection. Seven hundred and fifty-seven Italian participants completed an online survey between March 3rd to the 7th 2020, which was immediately before the lockdown. A moderated-mediation model was tested using a structural equation modeling approach. Results indicated that both Negative Affectivity and Right-Wing Authoritarianism were positively associated with COVID-19-related maladjusted behavior, and that Right-Wing Authoritarianism mediated the relationship between Negative Affectivity and maladjusted behavior. Furthermore, the effect of Right-Wing Authoritarianism on maladjusted behavior was greater for those with high anxiety of infection, and the indirect effect of Negative Affectivity on maladjusted behavior through Right-Wing Authoritarianism was moderated by infection anxiety. Findings highlight potential psychological paths that may inform communication strategies and public health initiatives aimed at promoting healthy behavior during an outbreak

[7,0]-metacyclophanes from biaryl coupling/macrocyclisation

The biaryl structural motif is a predominant feature in many pharmaceutically relevant and biologically active compounds. As a result, for over a century organic chemists have sought to develop new and more efficient aryl-aryl bond-forming methods (1). Cyclophanic natural products comprise an intriguing class of structurally diverse compounds. As inherent for all cyclic compounds regardless of their origin, macrocyclization is naturally the most decisive step, which defines the overall efficiency of the synthetic pathway. Especially in small cyclophanic molecules, this key step constitutes an even greater challenge. Due to the strain imparted by the macrocyclic system, free rotation of the benzene ring(s) is often restricted depending on both the constitution of the tether and the aromatic portions (2). Among cyclophanic natural products, the diarylheptanoids are a structurally sub-class with their scaffold consisting of two benzene rings tethered by an oxygenated aliphatic heptyl chain. In this work we reported different metal catalysed approaches to obtain the biaryl motif of myricanol, a natural [7,0]-metacyclophane with very important and recently discovered biological activities (3),(4),(5),(6). (Figure 1) Figure 1 The desired product 1could be obtained from the functionalized linear diarylheptanoid 2 by Suzuki domino process (macrocyclisation by linkage of aryl moieties) or could be synthesized from ring closing metathesis of product 3 which derived from a biaryl coupling of fragments 4 and 5. (1) Alberico, D.; Scott, M. E.; Lautens, M. Chem. Rev. 2007, 107 (1), 174–238. (2) Gulder, T.; Baran, P. S. Nat. Prod. Rep. 2012, 29 (8), 899-934. (3) Jones, J. R.; Lebar, M. D.; Jinwal, U. K.; Abisambra, J. F.; Koren, J.; Blair, L.; O’Leary, J. C.; Davey, Z.; Trotter, J.; Johnson, A. G.; Weeber, E.; Eckman, C. B.; Baker, B. J.; Dickey, C. A. J. Nat. Prod. 2011, 74 (1), 38–44. (4) Martin, M. D.; Calcul, L.; Smith, C.; Jinwal, U. K.; Fontaine, S. N.; Darling, A.; Seeley, K.; Wojtas, L.; Narayan, M.; Gestwicki, J. E.; Smith, G. R.; Reitz, A. B.; Baker, B. J.; Dickey, C. A. ACS Chem. Biol. 2015, 10 (4), 1099–1109. (5) Dai, G. H.; Meng, G. M.; Tong, Y. L.; Chen, X.; Ren, Z. M.; Wang, K.; Yang, F. Phytomedicine 2014, 21 (11), 1490–1496. (6) Dai, G.; Tong, Y.; Chen, X.; Ren, Z.; Ying, X.; Yang, F.; Chai, K. Int. J. Mol. Sci. 2015, 16 (2), 2717–2731

Cucumber mosaic virus Is Unable to Self-Assemble in Tobacco Plants When Transmitted by Seed

Cucumber mosaic virus (CMV), which has great impact on agronomic production worldwide, is both aphid and seed transmitted. Although the mechanisms of aphid transmission have been widely studied, those underlying the ability of CMV to survive and remain infectious during the passage from one generation to the next through the seeds are still to be clarified. Moreover, the viral determinants of seed transmission rate are poorly understood. Three viral genotypes produced from same RNA 1 and 2 components of CMV-Fny but differing in RNA 3 (the wild type CMV-Fny, a pseudorecombinant CMV-Fny/CMV-S and a chimeric CMV previously obtained by our group, named F, FS and CS, respectively) were propagated in Nicotiana tabacum cv Xanthi plants in order to assess differences in tobacco seed transmission rate and persistence through plant generations in the absence of aphid transmission. Seed-growth tests revealed CMV infection in the embryos, but not in the integuments. Seedlings from seed-growth tests showed the presence of all considered viruses but at different rates: from 4% (F, FS) to 16% (CS). Electron microscopy revealed absence (CS) of viral particles or virions without the typical central hole (F and FS). In agreement, structural characteristics of purified CMV particles, assessed by circular dichroism spectroscopy, showed anomalous spectra of nucleic acids rather than the expected nucleoproteins. These alterations resulted in no seed transmission beyond the first plant generation. Altogether, the results show for the first time that correct virion assembly is needed for seed infection from the mother plant but not to seedling invasion from the seed. We propose that incorrect virion formation, self-assembly and architecture stability might be explained if during the first stages of germination and seedling development some tobacco seed factors target viral regions responsible for protein-RNA interactions

The Conundrum of Cancer-Associated Thrombosis:Lesson Learned from Two Intriguing Cases and Literature Review

The correlation between cancer and venous thromboembolism (VTE) is solid, whereas the knowledge about cancer-related arterial thromboembolism (ATE) still needs a deeper investigation to clarify its pathogenesis. We describe two cases that represent useful hints for a comprehensive review of the thrombotic issue. A 75-year-old man with advanced rectal cancer treated with fluoropyrimidines suffered two catheter-related VTE events managed according to current guidelines. There was no indication for “extended” anticoagulant therapy for him, but during antithrombotic wash-out and fluoropyrimidines plus panitumumab regimen, he suffered a massive right coronary artery (RCA) thrombosis. Another patient with no cardiovascular (CV) risk factors and affected by advanced bladder cancer was treated with a platinum-containing regimen and suffered an acute inferior myocardial infarction 2 days after chemotherapy administration. He was successfully treated with primary Percutaneous Transluminal Coronary Angioplasty of RCA, discontinuing platinum-based therapy. Our observations raise the issue of cancer-associated thrombosis (CAT) complexity and the potential correlation between arterial and venous thrombotic events. Moreover, physicians should be aware of the thrombotic risk associated with anticancer therapies, suggesting that an appropriate prophylaxis should be considered

The Conundrum of Cancer-Associated Thrombosis:Lesson Learned from Two Intriguing Cases and Literature Review

The correlation between cancer and venous thromboembolism (VTE) is solid, whereas the knowledge about cancer-related arterial thromboembolism (ATE) still needs a deeper investigation to clarify its pathogenesis. We describe two cases that represent useful hints for a comprehensive review of the thrombotic issue. A 75-year-old man with advanced rectal cancer treated with fluoropyrimidines suffered two catheter-related VTE events managed according to current guidelines. There was no indication for “extended” anticoagulant therapy for him, but during antithrombotic wash-out and fluoropyrimidines plus panitumumab regimen, he suffered a massive right coronary artery (RCA) thrombosis. Another patient with no cardiovascular (CV) risk factors and affected by advanced bladder cancer was treated with a platinum-containing regimen and suffered an acute inferior myocardial infarction 2 days after chemotherapy administration. He was successfully treated with primary Percutaneous Transluminal Coronary Angioplasty of RCA, discontinuing platinum-based therapy. Our observations raise the issue of cancer-associated thrombosis (CAT) complexity and the potential correlation between arterial and venous thrombotic events. Moreover, physicians should be aware of the thrombotic risk associated with anticancer therapies, suggesting that an appropriate prophylaxis should be considered

Would You Prescribe Mobile Health Apps for Heart Failure Self-care? An Integrated Review of Commercially Available Mobile Technology for Heart Failure Patients

Treatment of chronic diseases, such as heart failure, requires complex protocols based on early diagnosis; self-monitoring of symptoms, vital signs and physical activity; regular medication intake; and education of patients and caregivers about relevant aspects of the disease. Smartphones and mobile health applications could be very helpful in improving the efficacy of such protocols, but several barriers make it difficult to fully exploit their technological potential and produce clear clinical evidence of their effectiveness. App suppliers do not help users distinguish between useless/dangerous apps and valid solutions. The latter are few and often characterised by rapid obsolescence, lack of interactivity and lack of authoritative information. Systematic reviews can help physicians and researchers find and assess the 'best candidate solutions' in a repeatable manner and pave the way for well-grounded and fruitful discussion on their clinical effectiveness. To this purpose, the authors assess 10 apps for heart failure self-care using the Intercontinental Marketing Statistics score and other criteria, discuss the clinical effectiveness of existing solutions and identify barriers to their use in practice and drivers for change