Theoretical investigations of supramolecular chemisorption adducts of volatile small molecules with a trinuclear silver(I) nitrated pyrazolate complex: DFT modeling of dipole-quadrupole interactions

Theoretical investigations of supramolecular chemisorption adducts of volatile small molecules with a trinuclear silver(I) nitrated pyrazolate complex: DFT modeling of dipole-quadrupole interactions Sammer M Tekarli1, [email protected], Vladimir N Nesterov1, Mohammad A Omary1, Rossana Galassi2, Simone Ricci2, Alfredo Burini2. (1) Department of Chemistry, University of North Texas, Denton, Texas 76203, United States, (2) School of Science and Technology, University of Camerino - Via Sant’Agostino, Camerino, Macerata I-62032, Italy A comparative study on the tendency of a new trinuclear silver(I) pyrazolate, namely [N,N-(3,5-dinitro-pyrazolate)Ag]3 (1) and a similar compound known previously, [N,N-(3,5-bis(trifluoromethyl)pyrazolate)Ag]3 (2) to adsorb small volatile molecules was performed. It was found that 1 has a remarkable tendency to form adducts, at room temperature and atmospheric pressure, with acetone, acetylacetone, ammonia, pyridine, acetonitrile, triethylamine, dimethylsulfide, and tetrahydrothiophene while CO, THF, alcohols, and diethyl ether were not adsorbed. On the contrary, 2 did not undergo adsorption of any of the aforementioned volatile molecules. Density Functional Theory (DFT) results (polarizability, electrostatic potential profiles, kinetics and thermodynamics, and positive point charge calculations) are consistent with the chemisorption model, explain the experimental adsorption selectivity for 1, and the lack of similar adsorption by 2 upon proper selection of the density functional. The M06 method in conjunction with CEP-31G basis set provides good agreement with the experimental data both qualitatively and quantitatively compared to B3LYP/CEP-31G. The results suggest that the adsorption of Lewis basic vapors occurs mainly by kinetic effects. The high vs. low binding energies calculated for the adducts of 1 with acetonitrile vs. CO manifest the experimental findings. The findings in this project suggest that this class of quadrupolar macromolecular complexes may exhibit potential for toxic industrial chemical (TIC) removal applications already known for porous organic polymers

Cultura tributaria y su incidencia en el cumplimiento de las obligaciones tributarias de microempresarios, mercado 28 de julio, Jaén, 2021

La investigación tuvo como objetivo general: Determinar la incidencia de la cultura tributaria en el cumplimiento de sus obligaciones tributarias de los microempresarios, mercado 28 de julio, Jaén,2021; investigación aplicada con enfoque cuantitativo de nivel descriptivo – correlacional, de diseño no experimental, donde se utilizó el cuestionario y para el análisis de datos el estadístico SPSS V-25 utilizando el Chi- cuadrado de Pearson. La muestra investigada fue de 55 Microempresarios del Mercado 28 de Julio de Jaén, a quienes se le aplicó dos cuestionarios, resultado que: el nivel de cultura tributaria es medio con el 70´9% el nivel de cumplimiento de las obligaciones tributarias es medio con 76,4%; existe incidencia significativa entre las dimensiones: conciencia tributaria y el cumplimiento de las obligaciones tributarias el valor de Chi-cuadrado es 27.466 con p=0.00<0.05; conocimiento tributario y el cumplimiento de obligaciones tributarias el valor de Chi-cuadrado 17.193, con p=0.00< 0.05; educación tributaria y el cumplimiento de las obligaciones tributarias el valor de Chi-cuadrado 10,882, con p= 0.00 < 0.05 concluyendo que existe incidencia significativa entre la cultura tributaria y el cumplimiento de las obligaciones tributarias, siendo el valor r= 25,443 para la Chi-cuadrado como significancia de p=0.00 < 0.05, aceptándose la hipótesis de investigación

Cupriphication of gold to sensitize d10–d10 metal–metal bonds and near-unity phosphorescence quantum yields

Outer-shell s0/p0 orbital mixing with d10 orbitals and symmetry reductionuponcupriphicationofcyclic trinucleartrigonal-planargold(I) complexes are found to sensitize ground-state Cu(I)–Au(I) covalent bonds and near-unity phosphorescence quantum yields. Heterobimetallic Au4Cu2 {[Au4(μ-C2,N3-EtIm)4Cu2(μ-3,5-(CF3)2Pz)2], (4a)}, Au2Cu {[Au2(μ-C2,N3-BzIm)2Cu(μ-3,5-(CF3)2Pz)], (1) and [Au2(μ-C2, N3-MeIm)2Cu(μ-3,5-(CF3)2Pz)], (3a)}, AuCu2 {[Au(μ-C2,N3-MeIm)Cu2(μ3,5-(CF3)2Pz)2], (3b) and [Au(μ-C2,N3-EtIm)Cu2(μ-3,5-(CF3)2Pz)2], (4b)} and stacked Au3/Cu3 {[Au(μ-C2,N3-BzIm)]3[Cu(μ-3,5-(CF3)2Pz)]3, (2)} formuponreactingAu3 {[Au(μ-C2,N3-(N-R)Im)]3 ((N-R)Im = imidazolate; R =benzyl/methyl/ethyl =BzIm/MeIm/EtIm)} with Cu3 {[Cu(μ-3,5(CF3)2Pz)]3 (3,5-(CF3)2Pz = 3,5-bis(trifluoromethyl)pyrazolate)}. The crystal structures of 1 and 3a reveal stair-step infinite chains whereby adjacent dimer-of-trimer units are noncovalently packed via twoAu(I)⋯Cu(I)metallophilicinteractions,whereas 4a exhibitsa hexanuclear cluster structure wherein two monomer-of-trimer units are linked by a genuine d10–d10 polar-covalent bond with ligandunassisted Cu(I)–Au(I) distances of 2.8750(8) Å each—the shortest such an intermolecular distance ever reported between any two d10 centers so as to deem it a “metal–metal bond” vis-à-vis “metallophilic interaction.” Density-functional calculations estimate 35– 43kcal/molbindingenergy,akintotypicalM–Msingle-bondenergies. Congruently, FTIR spectra of4a showmultiple far-IR bands within 65– 200 cm−1, assignable to vCu-Au as validated by both the Harvey–Gray method of crystallographic-distance-to-force-constant correlation and dispersive density functional theory computations. Notably, the heterobimetallic complexes herein exhibit photophysical properties that are favorable to those for their homometallic congeners, due to threefold-to-twofold symmetry reduction, resulting in cuprophilicsensitizationinextinctioncoefficientandsolid-state photoluminescence quantum yields approaching unity (ΦPL = 0.90–0.97 vs. 0–0.83 for Au3 and Cu3 precursors), which bodes well for potential future utilization in inorganic and/or organic LED applications

The Impact of Lifestyle Interventions in High-Risk Early Breast Cancer Patients: A Modeling Approach from a Single Institution Experience

none21noA healthy lifestyle plays a strategic role in the prevention of BC. The aim of our prospective study is to evaluate the effects of a lifestyle interventions program based on special exercise and nutrition education on weight, psycho-physical well-being, blood lipid and hormonal profile among BC patients who underwent primary surgery. From January 2014 to March 2017, a multidisciplinary group of oncologists, dieticians, physiatrists and an exercise specialist evaluated 98 adult BC female patients at baseline and at different time points. The patients had at least one of the following risk factors: BMI ≥ 25 Kg/m2, high testosterone levels, high serum insulin levels or diagnosis of MS. Statistically significant differences are shown in terms of BMI variation with the lifestyle interventions program, as well as in waist circumference and blood glucose, insulin and testosterone levels. Moreover, a statistically significant difference was reported in variations of total Hospital Anxiety and Depression Scale (HADS) score, in the anxiety HADS score and improvement in joint pain. Our results suggested that promoting a healthy lifestyle in clinical practice reduces risk factors involved in BC recurrence and ensures psycho-physical well-being.openMirco Pistelli, Valentina Natalucci, Laura Scortichini, Veronica Agostinelli, Edoardo Lenci, Sonia Crocetti, Filippo Merloni, Lucia Bastianelli, Marina Taus, Daniele Fumelli, Gloria Giulietti, Claudia Cola, Marianna Capecci, Roberta Serrani, Maria Gabriella Ceravolo, Maurizio Ricci, Albano Nicolai, Elena Barbieri, Giulia Nicolai, Zelmira Ballatore, Agnese Savini and Rossana BerardiPistelli, Mirco; Natalucci, Valentina; Scortichini, Laura; Agostinelli, Veronica; Lenci, Edoardo; Crocetti, Sonia; Merloni, Filippo; Bastianelli, Lucia; Taus, Marina; Fumelli, Daniele; Giulietti, Gloria; Cola, Claudia; Capecci, Marianna; Serrani, Roberta; Gabriella Ceravolo, Maria; Ricci, Maurizio; Nicolai, Albano; Barbieri, Elena; Nicolai, Giulia; Ballatore, Zelmira; Savini and Rossana Berardi, Agnes

Sunitinib in patients with pre-treated pancreatic neuroendocrine tumors: A real-world study

Introduction: Besides data reported in a Phase-III trial, data on sunitinib in pancreatic Neuroendocrine Tumors (panNETs) are scanty. Aim: To evaluate sunitinib efficacy and tolerability in panNETs patients treated in a real-world setting. Patients and methods: Retrospective analysis of progressive panNETs treated with sunitinib. Efficacy was assessed by evaluating progression-free survival, overall survival, and disease control (DC) rate (stable disease (SD) + partial response + complete response). Data are reported as median (25th\ue2\u80\u9375th IQR). Results: Eighty patients were included. Overall, 71.1% had NET G2, 26.3% had NET G1, and 2.6% had NET G3 neoplasms. A total of 53 patients (66.3%) had received three or more therapeutic regimens before sunitinib, with 24 patients (30%) having been treated with four previous treatments. Median PFS was 10 months. Similar risk of progression was observed between NET G1 and NET G2 tumors (median PFS 11 months and 8 months, respectively), and between patients who had received \ue2\u89\ua5 3 vs \ue2\u89\ua4 2 therapeutic approaches before sunitinib (median PFS 9 months and 10 months, respectively). DC rate was 71.3% and SD was the most frequent observed response, occurring in 43 pts (53.8%). Overall, 59 pts (73.8%) experienced AEs, which were grade 1\ue2\u80\u932 in 43 of them (72.9%), grade 3 in 15 pts (25.4%), and grade 4 in one patient (1.7%). Six pts (7.5%) stopped treatment due to toxicity. Conclusions: The present real-world experience shows that sunitinib is a safe and effective treatment for panNETs, even in the clinical setting of heavily pre-treated, progressive diseases

Ethical Criteria for the Admission and Management of Patients in the ICU Under Conditions of Limited Medical Resources: A Shared International Proposal in View of the COVID-19 Pandemic

Introduction The present pandemic has exposed us to unprecedented challenges that need to be addressed not just for the current state, but also for possible future similar occurrences. It is worth pointing out that discussions on the allocation of medical resources may not necessarily refer to an exception, but, unfortunately, to a regular condition for a large part of humanity (1). The criteria for admission to an Intensive Care Unit (ICU) setting generally take into account multiple factors. There must be a diagnostic and prognostic basis for the decisions made, considering both biological factors and patient values and wishes. Furthermore, the decision-making process should, whenever possible, respect the patient's advance directives as well as the relationship with the patient's family or attorney. Therapeutic neglect should be avoided. Having applied standard clinical evaluation criteria for the appropriate treatment of patients with COVID-19, including consideration of prognosis, if a hospital then finds itself unable to provide optimal treatment (e.g., due to a disproportion between the number of patients and the availability of beds, healthcare providers, ventilators, and drugs in the ICU), it becomes necessary to evaluate, case by case, how to achieve justice and the best possible good for the greatest number of patients. It is therefore mandatory to explore alternative solutions; these include increasing available beds and healthcare providers, implementing alternative, though suboptimal, approaches (where appropriate), transferring patients to other clinical units, etc. Making these decisions properly also involves the recovery of the political role of medicine and science (2). If the imbalance between needs and resources reaches a critical level, an emergency triage protocol, following the operational and ethical indications of “disaster medicine,” should be activated. These have been deployed in major and serious natural (earthquakes or tsunamis for example) and technological (factory explosions, public transport accidents for example) disasters, as well as following terrorist attacks (3, 4). The question of the feasibility of developing a clinical evaluation algorithm to support the decision-making of the triage team remains open, though many such protocols have been written. According to the above, we propose the following five ethical criteria for the triage of patients in conditions of limited resources, such as the COVID pandemic. They are the result of an interdisciplinary and intercultural dialogue between specialists from different disciplines. Several of the authors are working in the main epicenters of the crisis and currently are playing a central role in the bioethical, clinical, social and legal aspects of the management of the COVID-19 pandemic

Development and implementation of the AIDA International Registry for patients with Periodic Fever, Aphthous stomatitis, Pharyngitis, and cervical Adenitis syndrome

Objective: Aim of this paper is to illustrate the methodology, design, and development of the AutoInflammatory Disease Alliance (AIDA) International Registry dedicated to patients with the Periodic Fever, Aphthous stomatitis, Pharyngitis, and cervical Adenitis (PFAPA) syndrome. Methods: This is a physician-driven, non-population- and electronic-based registry proposed to gather real-world demographics, clinical, laboratory, instrumental and socioeconomic data from PFAPA patients. Data recruitment is realized through the on-line Research Electronic Data Capture (REDCap) tool. This registry is thought to collect standardized information for clinical research leading to solid real-life evidence. The international scope and the flexibility of the registry will facilitate the realization of cutting-edge study projects through the constant updating of variables and the possible merging and transfer of data between current and future PFAPA registries. Results: A total of 112 centers have already been involved from 23 countries and 4 continents starting from August 24th, 2021, to April 6th, 2022. In total 56/112 have already obtained the formal approval from their local Ethics Committees. The platform counts 321 users (113 principal investigators, 203 site investigators, two lead investigators, and three data managers). The registry collects retrospective and prospective data using 3,856 fields organized into 25 instruments, including PFAPA patient's demographics, medical histories, symptoms, triggers/risk factors, therapies, and impact on the healthcare systems. Conclusions: The development of the AIDA International Registry for PFAPA patients will enable the on-line collection of standardized data prompting real-life studies through the connection of worldwide groups of physicians and researchers. This project can be found on NCT 05200715

Defining Kawasaki disease and pediatric inflammatory multisystem syndrome-temporally associated to SARS-CoV-2 infection during SARS-CoV-2 epidemic in Italy: results from a national, multicenter survey

Background: There is mounting evidence on the existence of a Pediatric Inflammatory Multisystem Syndrome-temporally associated to SARS-CoV-2 infection (PIMS-TS), sharing similarities with Kawasaki Disease (KD). The main outcome of the study were to better characterize the clinical features and the treatment response of PIMS-TS and to explore its relationship with KD determining whether KD and PIMS are two distinct entities. Methods: The Rheumatology Study Group of the Italian Pediatric Society launched a survey to enroll patients diagnosed with KD (Kawasaki Disease Group - KDG) or KD-like (Kawacovid Group - KCG) disease between February 1st 2020, and May 31st 2020. Demographic, clinical, laboratory data, treatment information, and patients' outcome were collected in an online anonymized database (RedCAP®). Relationship between clinical presentation and SARS-CoV-2 infection was also taken into account. Moreover, clinical characteristics of KDG during SARS-CoV-2 epidemic (KDG-CoV2) were compared to Kawasaki Disease patients (KDG-Historical) seen in three different Italian tertiary pediatric hospitals (Institute for Maternal and Child Health, IRCCS "Burlo Garofolo", Trieste; AOU Meyer, Florence; IRCCS Istituto Giannina Gaslini, Genoa) from January 1st 2000 to December 31st 2019. Chi square test or exact Fisher test and non-parametric Wilcoxon Mann-Whitney test were used to study differences between two groups. Results: One-hundred-forty-nine cases were enrolled, (96 KDG and 53 KCG). KCG children were significantly older and presented more frequently from gastrointestinal and respiratory involvement. Cardiac involvement was more common in KCG, with 60,4% of patients with myocarditis. 37,8% of patients among KCG presented hypotension/non-cardiogenic shock. Coronary artery abnormalities (CAA) were more common in the KDG. The risk of ICU admission were higher in KCG. Lymphopenia, higher CRP levels, elevated ferritin and troponin-T characterized KCG. KDG received more frequently immunoglobulins (IVIG) and acetylsalicylic acid (ASA) (81,3% vs 66%; p = 0.04 and 71,9% vs 43,4%; p = 0.001 respectively) as KCG more often received glucocorticoids (56,6% vs 14,6%; p &lt; 0.0001). SARS-CoV-2 assay more often resulted positive in KCG than in KDG (75,5% vs 20%; p &lt; 0.0001). Short-term follow data showed minor complications. Comparing KDG with a KD-Historical Italian cohort (598 patients), no statistical difference was found in terms of clinical manifestations and laboratory data. Conclusion: Our study suggests that SARS-CoV-2 infection might determine two distinct inflammatory diseases in children: KD and PIMS-TS. Older age at onset and clinical peculiarities like the occurrence of myocarditis characterize this multi-inflammatory syndrome. Our patients had an optimal response to treatments and a good outcome, with few complications and no deaths

First World Consensus Conference on pancreas transplantation: Part II - recommendations.

Funder: Fondazione Pisa, Pisa, Italy; Id: http://dx.doi.org/10.13039/100007368Funder: Tuscany Region, Italy; Id: http://dx.doi.org/10.13039/501100009888Funder: Pisa University Hospital, Pisa, ItalyFunder: University of Pisa, Pisa, Italy; Id: http://dx.doi.org/10.13039/501100007514The First World Consensus Conference on Pancreas Transplantation provided 49 jury deliberations regarding the impact of pancreas transplantation on the treatment of diabetic patients, and 110 experts' recommendations for the practice of pancreas transplantation. The main message from this consensus conference is that both simultaneous pancreas-kidney transplantation (SPK) and pancreas transplantation alone can improve long-term patient survival, and all types of pancreas transplantation dramatically improve the quality of life of recipients. Pancreas transplantation may also improve the course of chronic complications of diabetes, depending on their severity. Therefore, the advantages of pancreas transplantation appear to clearly surpass potential disadvantages. Pancreas after kidney transplantation increases the risk of mortality only in the early period after transplantation, but is associated with improved life expectancy thereafter. Additionally, preemptive SPK, when compared to SPK performed in patients undergoing dialysis, appears to be associated with improved outcomes. Time on dialysis has negative prognostic implications in SPK recipients. Increased long-term survival, improvement in the course of diabetic complications, and amelioration of quality of life justify preferential allocation of kidney grafts to SPK recipients. Audience discussions and live voting are available online at the following URL address: http://mediaeventi.unipi.it/category/1st-world-consensus-conference-of-pancreas-transplantation/246