Deciphering the Role of Crown-ether Receptor Orientation in C-H Oxidation Catalyzed by Supramolecular Nonheme FeIV(O) Complexes.

The outstanding efficiency and selectivity of enzymatic reactions, such as C-H oxidation by nonheme iron oxygenases, stems from a precise control of substrate positioning inside the active site. The resulting proximity between a specific moiety (a certain C-H bond) to the reactant (a FeIV(O) active species) translates into higher rates and selectivity, that can be in part replicated also with artificial supramolecular catalysts. However, structural modification of the position and orientation of the binding site both in enzymes and in artificial catalysts often leads to significant variations in reactivity that can be difficult to rationalize due to the system's complexity.

Aprotic electrolytes beyond organic carbonates: transport properties of LiTFSI solutions in sulphur based solvents.

This work illustrates a physico-chemical study of the structural, dynamic, and transport properties of electrolytes made of LiTFSI solutions in sulphoxide and sulphone solvent mixtures. Experimental measurements, by Raman and NMR spectroscopies, as well as electrochemical impedance spectroscopy, reveal the formation of a variety of ionic aggregates depending on the solvent composition that significantly affect the ion mobility and conductivity of the electrolyte. Mixtures containing tetrahydrothiophene-1-oxide exhibit a larger ion mobility due to a rapid exchange mechanism between solvent molecules, whereas the use of tetramethylene sulphone favors the formation of ionic aggregates due to the strong dipolar interactions between solvent molecules.

-Iridoids: Occurrence, Chemophenetic Evaluation and Biological Activities-A Review.

In this work, the first review paper about -iridoids was presented. In particular, their detailed occurrence, chemophenetic evaluation and biological activities were reported. To the best of our knowledge, two hundred and eighty-eight -iridoids have been evidenced so far, bearing different structural features, with the link between two -iridoids sub-units as the major one.

Lesson in understanding parents' perspective: perception of quality of care and COVID-19-related fears among users of paediatric health services over the COVID-19 pandemic in 11 facilities in Italy.

Background: The COVID-19 pandemic had an important psychological impact on children and their families. This study aims to explore paediatric health services users' perceptions of quality of care (QOC) and COVID-19-related fears, and their evolution over time in relation to COVID-19 pandemic.

Methods: In a multicentre cross-sectional study involving 11 public hospitals providing paediatric care across the Italian territory, we collected data from services users through a validated questionnaire.

The Relationship of Frailty with Psychopathology, Childhood Traumas and Insecure Attachment in Young Adults: A Cross-Sectional Investigation.

Objective: Reciprocal connections exist between mental health and physical health, and conditions of cellular senescence/advanced biological age have been observed in association with certain psychiatric diseases. However, the construct of frailty has only preliminarily been explored in young adults and in relation to psychopathology so far. In the present study we aimed at further elucidating the relationships linking psychopathological phenomena with physical diseases in a sample of young adults.

Artificial Intelligence for Mechanical Ventilation: A Transformative Shift in Critical Care.

With the large volume of data coming from implemented technologies and monitoring systems, intensive care units (ICUs) represent a key area for artificial intelligence (AI) application. Despite the last decade has been marked by studies focused on the use of AI in medicine, its application in mechanical ventilation management is still limited. Optimizing mechanical ventilation is a complex and high-stake intervention, which requires a deep understanding of respiratory pathophysiology.

Maintenance immunosuppressive therapy in liver transplantation: results from CESIT study, an Italian retrospective cohort study.

Objectives: To investigate the use of maintenance immunosuppressive treatments following liver transplantation and to compare their risk-benefit profiles in clinical practice.

Design: Retrospective multicentrer cohort study.

Setting: Four Italian regions (Lombardy, Veneto, Lazio, Sardinia).

Adherence to the 2019 ESC/EAS guidelines for dyslipidaemia management in a large rheumatoid arthritis cohort: Data from the CORDIS Study Group of the Italian Society of Rheumatology.

Background/aim: Lipid-lowering therapy prescription is low in rheumatoid arthritis (RA) patients, often not achieving lipid threshold target despite treatment. However, evidence derives from small, monocentric cohorts. We assessed adherence to lipid-lowering treatment for primary cardiovascular (CV) prevention in a RA cohort according to international guidelines.

SICOB Italian clinical practice guidelines for the surgical treatment of obesity and associated diseases using GRADE methodology on bariatric and metabolic surgery.

Obesity is a chronic disease associated with increased morbidity and mortality and reduced quality of life. Pharmacotherapy can be associated with life style changes in increasing and maintaining weight loss and ameliorating obesity-related complications and comorbidities. In patients affected by obesity and uncontrolled obesity-associated complications or high degrees of BMI (> 40 Kg/m), metabolic bariatric surgery can be a valid therapeutic option.

The interplay between the urban development of Rome (Italy) and the Tiber River floods: A review of two millennia of socio-hydrological history.

The urban development of Rome (Italy) has been intertwined with the dynamics of the Tiber River since its foundation. In this review paper, we analyse more than 2500 years of flood history and urban development to untangle the dynamics of flood risk and assess the resulting socio-hydrological phenomena. Until the 1800s, urban dwellers living in the riparian areas of the Tiber River were accustomed to frequent flooding.

Mechanisms in the Synthesis of S-Alcohols with 1,4-NADH Biomimetic Co-factor N-Benzyl-1,4-dihydronicotinamide using Horse Liver Alcohol Dehydrogenase: A Hybrid Computational Study.

The enantioselective reduction of prochiral ketones catalyzed by horse liver alcohol dehydrogenase (HLADH), was investigated via a hybrid computational approach, for molecular reactions involved in chiral synthesis of S-alcohols, when the natural co-factor, 1,4-dihyronicotinamide adenine dinucleotide, 1,4-NADH, was replaced with biomimetic co-factor, N-benzyl-1,4-dihydronicotinamide, 1. We surmised that different hydride and proton transfer mechanisms were involved using co-factor, 1. An alternative mechanism, where the hydride transfer step occurred, via an η-keto-S-η-5,6-1,4-dihydronicotinamide-Zn(II) complex, was previously investigated with a model of the HLADH-Zn(II) catalytic site (J.

A survey of VKORC1 missense mutations in eleven Italian islands reveals widespread rodenticide resistance in house mice.

To protect native wildlife, more than one hundred rodent eradications have been attempted in the Mediterranean islands by using anticoagulant rodenticides (ARs). Despite their high efficiency, resistance to ARs has been observed in many countries and it is mostly related to missense mutations (SNPs) in the VKORC1 gene. The presence of resistant individuals reduces the efficiency of rodent management, leading to an excessive use of ARs.

Multiparametric ultrasound evaluation of thyroid nodules.

Thyroid nodules are common incidental findings. Most of them are benign, but many unnecessary fine-needle aspiration procedures, core biopsies, and even thyroidectomies or non-invasive treatments have been performed. To improve thyroid nodule characterization, the use of multiparametric ultrasound evaluation has been encouraged by most experts and several societies.

In-Depth XANES and EXAFS Characterization of the Ag Ion Coordination in Dimethyl Sulfoxide Solution.

X-ray absorption near-edge structure (XANES) spectroscopy has been used, in conjunction with extended X-ray absorption fine structure (EXAFS), to determine the coordination structure of the Ag ion in a dimethyl sulfoxide (DMSO) solution. From the EXAFS data analysis, the Ag-O first shell distance in DMSO was found to be 2.31(3) Å, with 4.

Non-empirical peak shape methods based on the physical model of the one trap one recombination center model.

Any experimental Thermoluminescent (TL) glow-peak contains the activation energy information of its corresponding energy level within the band gap in insulating materials. The theory of peak shape methods (PSM) correlates the macroscopic geometrical characteristics of a single TL peak with activation energy of the level responsible for the TL peak by assuming that the area under a TL peak can be approximated by the area of a triangle. In this way the geometrical characteristics becomes the measure of the activation energy.

Correlating Ultrastability with Fragility and Surface Mobility in Vapor Deposited Tetrahedral Glasses.

Several experiments on molecular and metallic glasses have shown that the ability of vapor deposition to produce ultrastable glasses is correlated to their structural and thermodynamic properties. Here we investigate the vapor deposition of a class of tetrahedral materials (including silicon and water) via molecular dynamics simulations of the generalized Stillinger-Weber potential. By changing a single parameter that controls the local tetrahedrality, we show that the emergence of ultrastable behavior is correlated with an increase in the fragility of the model.

Dosimetry of microbeam radiotherapy by flexible hydrogenated amorphous silicon detectors.

Detectors that can provide accurate dosimetry for microbeam radiation therapy (MRT) must possess intrinsic radiation hardness, a high dynamic range, and a micron-scale spatial resolution. In this work we characterize hydrogenated amorphous silicon detectors for MRT dosimetry, presenting a novel combination of flexible, ultra-thin and radiation-hard features.Two detectors are explored: an n-type/intrinsic/p-type planar diode (NIP) and an NIP with an additional charge selective layer (NIP + CSC).