Benchmarking dispersion-corrected DFT methods for the evaluation of materials with anisotropic properties: structural, electronic, dielectric, optical and vibrational analysis of calcite (CaCO3, space group R3[combining macron]c).

Calcite (CaCO3, space group R3[combining macron]c) is a solid phase whose well-known highly anisotropic physical properties can be exploited to compare and calibrate various theoretical simulation methods. In this work, to benchmark different ab initio Density Functional Theory approaches that include for the first time corrections for dispersive forces, a systematic analysis of structural, electronic, dielectric, optical and vibrational properties of calcite is performed. The simulations considered the generalized-gradient approximation functional PBE and the hybrid B3LYP and PBE0, whereas the DFT-D2 and DFT-D3 schemes were adopted to account for the long-range interactions. This study suggests an overall better agreement between the theoretical results obtained with the DFT functionals corrected for the dispersive forces, with a better performance of hybrid functionals over PBE.

La Dolce Vita in times of harshness: Prevalence of health-related behaviors during the great recession in Italy.

The current work investigates the heterogeneous effect of the 2008 recession on health outcomes in the Italian population across the main geographic areas. Health outcomes were proxied by individual-level information on healthy/risky behaviors, such as individual fruit and vegetable consumption, frequency of bodyweight monitoring, smoking, and alcohol intake. These health outcomes were employed as dependent variables in the empirical model that included some socioeconomic individual aspects (e.g., age, gender, education, and income source), as well as consumer price index data for tobacco products, alcoholic beverages, and fruit and vegetables. In this work, we used twelve years of data (2005-2016) from the Italian Multipurpose Household Survey (MHS), which collects individual self-reported characteristics, augmented with information on unemployment rates at the regional level, as well as with consumer price indexes for the goods analyzed. The results indicated that the 2008 economic crisis lowered the probability that individuals engage in healthy behaviors, such as self-monitoring their bodyweight, mostly among individuals in northern and central areas. Likewise, the economic downturn increased the probability of smoking regardless of the geographic area, with a larger magnitude in individuals in northern and central areas, whose health outcomes were more impacted by the economic downturn than individuals living in the southern and island areas.

Hydroxylapatite and Related Minerals in Bone and Dental Tissues: Structural, Spectroscopic and Mechanical Properties from a Computational Perspective.

Hard tissues (e.g., bone, enamel, dentin) in vertebrates perform various and different functions, from sustaining the body to haematopoiesis. Such complex and hierarchal tissue is actually a material composite whose static and dynamic properties are controlled by the subtle physical and chemical interplay between its components, collagen (main organic part) and hydroxylapatite-like mineral. The knowledge needed to fully understand the properties of bony and dental tissues and to develop specific applicative biomaterials (e.g., fillers, prosthetics, scaffolds, implants, etc.) resides mostly at the atomic scale. Among the different methods to obtains such detailed information, atomistic computer simulations (in silico) have proven to be both corroborative and predictive tools in this subject. The authors have intensively worked on quantum mechanical simulations of bioapatite and the present work reports a detailed review addressed to the crystal-chemical, physical, spectroscopic, mechanical, and surface properties of the mineral phase of bone and dental tissues. The reviewed studies were conducted at different length and time scales, trying to understand the features of hydroxylapatite and biological apatite models alone and/or in interaction with simplified collagen-like models. The reported review shows the capability of the computational approach in dealing with complex biological physicochemical systems, providing accurate results that increase the overall knowledge of hard tissue science.

Electrochemical data on redox properties of human Cofilin-2 and its Mutant S3D.

The reported data are related to a research paper entitled "Phosphorylated cofilin-2 is more prone to oxidative modifications on Cys39 and favors amyloid fibril formation" [1]. Info about the formation and redox properties of the disulfide bridge of a protein is quite difficult to obtain and only in a few cases was it possible to observe a cyclic voltammetry (CV) signal [2,3]. Human cofilin-2 contains two cysteines (Cys39 and Cys80) which can be oxidized in suitable conditions and form a disulfide bridge [1]. For this purpose, CV measurements were carried out on human cofilin-2 WT and its mutant S3D immobilized on a gold electrode coated by an anionic self-assembled monolayer (SAM), after a pre-oxidation time which was fundamental for observing a CV signal relating to the oxidation/reduction process of the disulfide bridge of the proteins. The data include CV curves obtained with and without electrochemical pre-oxidation and after oxidation with H2O2. In addition, the plot of the cathodic peak current vs. electrochemical pre-oxidation time and the pH dependence of the formal potential (E°') are reported. The data obtained by CV measurements were used to determine the time required to form the disulfide bridge for the immobilized proteins and, consequently, to observe the CV signal, to calculate the E°' values and analyse the pH dependence of E°'. The electrochemical data were provided which will be useful for further electrochemical investigations regarding proteins bearing disulfide bridge(s) or cysteines prone to oxidation.

Phosphorylated cofilin-2 is more prone to oxidative modifications on Cys39 and favors amyloid fibril formation.

Cofilins are small protein of the actin depolymerizing family. Actin polymerization/depolymerization is central to a number of critical cellular physiological tasks making cofilin a key protein for several physiological functions of the cell. Cofilin activity is mainly regulated by phosphorylation on serine residue 3 making this post-translational modification key to the regulation of myofilament integrity. In fact, in this form, the protein segregates in myocardial aggregates in human idiopathic dilated cardiomyopathy. Since myofilament network is an early target of oxidative stress we investigated the molecular changes induced by oxidation on cofilin isoforms and their interplay with the protein phosphorylation state to get insight on whether/how those changes may predispose to early protein aggregation. Using different and complementary approaches we characterized the aggregation properties of cofilin-2 and its phosphomimetic variant (S3D) in response to oxidative stress in silico, in vitro and on isolated cardiomyocytes. We found that the phosphorylated (inactive) form of cofilin-2 is mechanistically linked to the formation of an extended network of fibrillar structures induced by oxidative stress via the formation of a disulfide bond between Cys39 and Cys80. Such phosphorylation-dependent effect is likely controlled by changes in the hydrogen bonding network involving Cys39. We found that the sulfide ion inhibits the formation of such structures. This might represent the mechanism for the protective effect of the therapeutic agent Na2S on ischemic injury.

Simulated infrared and Raman spectroscopy, complex dielectric function and refractive index dataset of monoclinic C2/m stoichiometric clinochlore Mg6Si4O10(OH)8 as obtained from Density Functional Theory.

This article reports a simulated dataset of the vibrational (infrared and Raman) and optical properties (complex dielectric function and refractive index) of clinochlore, an important mineral belonging to the phyllosilicate family [1]. The data here reported were calculated from ab initio Density Functional Theory (DFT) simulations at B3LYP level, including a correction for the dispersive forces (B3LYP-D* approach) and all-electron Gaussian-type orbitals basis sets. This dataset was calculated between 0 cm-1 and 4000 cm-1 and comprises infrared, reflectance and Raman spectra, frequency-dependent complex dielectric function and complex refractive index of clinochlore. The data was validated against available experimental spectroscopic results reported in literature and can be of help in several application fields, for instance fundamental georesource exploration and exploitation, in applied mineralogy, geology, material science, and as a reference to assess the quality of other theoretical approaches.

Stannous Fluoride Preventive Effect on Enamel Erosion: An In Vitro Study.

The aim of this in vitro study was to evaluate the effects of a single dose application of two daily toothpastes on enamel exposed to acid attack. The research was conducted on human molars enamel fragments (n = 72). The two different toothpastes active ingredients were sodium fluoride (NaF) and stannous fluoride (SnF2). They were compared in protecting the surface of the enamel exposed to three acids: citric acid, lactic acid and hydrochloric acid. A spectrophotometer was used to measure the calcium ions and phosphate released in the solutions by the enamel specimens. Afterward, ionic concentrations were analyzed through the t-Student test, in order to estimate the significance level (p < 0.05) of the solubility differences obtained between the treatment and control groups. Finally, sample surfaces were analyzed with scanning electron microscopy and X-ray energy dispersive spectroscopy (SEM/EDX). The two analyzed toothpastes did not reveal any statistically significant variation in the release of calcium and phosphate (p > 0.05). Nevertheless, acid-resistant deposits were detected in samples treated with stannous fluoride and exposed to lactic acid, though the presence of tin ion deposits on samples treated with stannous fluoride was not shown. A single dose of a fluoride-based toothpaste before different acids attack, in simulated oral cavity conditions, did not show a significant preventive effect.

Hydrocarbons in phlogopite from Kasenyi kamafugitic rocks (SW Uganda): cross-correlated AFM, confocal microscopy and Raman imaging.

This study presents a cross-correlated surface and near surface investigation of two phlogopite polytypes from Kasenyi kamafugitic rocks (SW Uganda) by means of advanced Atomic Force Microscopy (AFM), confocal microscopy and Raman micro-spectroscopy. AFM revealed comparable nanomorphology and electrostatic surface potential for the two mica polytypes. A widespread presence of nano-protrusions located on the mica flake surface was also observed, with an aspect ratio (maximum height/maximum width) from 0.01 to 0.09. Confocal microscopy showed these features to range from few nm to several µm in dimension, and shapes from perfectly circular to ellipsoidic and strongly elongated. Raman spectra collected across the bubbles showed an intense and convolute absorption in the range 3000-2800 cm-1, associated with weaker bands at 1655, 1438 and 1297 cm-1, indicating the presence of fluid inclusions consisting of aliphatic hydrocarbons, alkanes and cycloalkanes, with minor amounts of oxygenated compounds, such as carboxylic acids. High-resolution Raman images provided evidence that these hydrocarbons are confined within the bubbles. This work represents the first direct evidence that phlogopite, a common rock-forming mineral, may be a possible reservoir for hydrocarbons.

Single Molecule Investigation of Glycine-Chlorite Interaction by Cross-Correlated Scanning Probe Microscopy and Quantum Mechanics Simulations.

In this work, we studied the interaction of glycine with the (001) surface of chlorite mineral at a single molecule level by cross-correlating scanning probe microscopy (SPM) and ab initio quantum mechanics (QM) investigations. Chlorite mineral is particularly interesting and peculiar for the interaction with organic molecules because it presents an alternated stacking of brucite-like (hydrophobic) and talc-like (hydrophilic) layers of different polarities. Brucite-like is positive, whereas talc-like is negative. The experimental atomic force microscopy (AFM) observations show that glycine is stably and selectively adsorbed on the brucite-like layer, organized in monolayers with different patterns. The sizes of single molecules of glycine measured by AFM are in agreement with those calculated by QM. Glycine molecules were found to align both at the edges and on the terraces of the brucitic surface. QM simulations confirmed the AFM observations that glycine molecule is adsorbed with high adsorption energy preferentially with its plane parallel to the (001) brucite-like surface. QM also provided the geometry conformation of the molecule and the bonding scheme between glycine and brucite surface. This kind of data can be very helpful both to biotechnological applications of this substrate and to depict some important processes that might have been occurred in prebiotic environments.

Insights into the interaction between CH2F2 and titanium dioxide: DRIFT spectroscopy and DFT analysis of the adsorption energetics.

Difluoromethane (CH2F2, HFC-32) has been proposed as a valid replacement for both CFCs and HCFCs (in particular HCFC-22), and nowadays it is widely used in refrigerant mixtures. Due to its commercial use, in the last years, the atmospheric concentration of HFC-32 has increased significantly. However, this molecule presents strong absorptions within the 8-12µm atmospheric window, and hence it is a greenhouse gas which contributes to global warming. Heterogeneous photocatalysis over TiO2 surface is an interesting technology for removing atmospheric pollutants since it leads to the decomposition of organic compounds into simpler molecules. In the present work, the adsorbate-substrate interaction between CH2F2 and TiO2 is investigated by coupling experimental measurements using DRIFT spectroscopy to first-principle simulations at DFT/B3LYP level. The experimental results confirm that CH2F2 interacts with the TiO2 surface (∼80% rutile, 20% anatase) through both F and H atoms and show that the DRIFT technique is well suited to study the adsorption of halogenated methanes over semiconductor surfaces. DFT calculations are carried out by considering different periodicities and surface coverages, according to a structure involving an acid-base interaction between the F and Ti(4+) atoms as well as an H-bond between the CH2 group and an O(2-) ion. Lateral effects and energetics are analyzed in the limit of low coverage according to a procedure taking into account the binding, interaction, and distortion energies. The simulation at the different surface coverages and periodicities suggests similar decomposition pathways for the different investigated ensemble configurations.

Food for Healthy Living and Active Ageing.

The link between diet and health has been recognized since the Grecian period; as Hippocrates said, "Let food be your medicine and medicine be your food". Although the primary goals of diet are meeting nutritional requirements and providing energy, there is increasing awareness that a correct and balanced diet may prevent the insurgence of diet-related pathologies and/or improve well-being and life expectancy, also reflecting on the ageing process. Research on the interaction among nutrients, gut microbiota and host metabolism is presently unravelling the molecular mechanisms underlying the positive and negative effects of traditional diets on health and ageing, providing useful information for the design of innovative foods targeting specific needs and segments of the population. The food supply chain plays a key role in ensuring quality and safety through both comprehensive quality management and inspection systems and a focused innovation process mainly devoted to the creation of functional foods. However, innovation and scientific development pose a problem of information asymmetry towards final consumers; thus, regulatory aspects and private and public communication strategies must be efficiently developed.

3D finite element analysis of electrostatic deflection of commercial and FIB-modified cantilevers for electric and Kelvin force microscopy: I. Triangular shaped cantilevers with symmetric pyramidal tips.

The investigation of the nanoscale distribution of electrostatic forces on material surfaces is of paramount importance for the development of nanotechnology, since these confined forces govern many physical processes on which a large number of technological applications are based. For instance, electric force microscopy (EFM) and micro-electro-mechanical-systems (MEMS) are technologies based on an electrostatic interaction between a cantilever and a specimen. In the present work we report on a 3D finite element analysis of the electrostatic deflection of cantilevers for electric and Kelvin force microscopy. A commercial triangular shaped cantilever with a symmetric pyramidal tip was modelled. In addition, the cantilever was modified by a focused ion beam (FIB) in order to reduce its parasitic electrostatic force, and its behaviour was studied by computation analysis. 3D modelling of the electrostatic deflection was realized by using a multiphysics finite element analysis software and it was applied to the real geometry of the cantilevers and probes obtained by using basic CAD tools. The results of the modelling are in good agreement with experimental data.

3D finite element analysis of electrostatic deflection and shielding of commercial and FIB-modified cantilevers for electric and Kelvin force microscopy: II. Rectangular shaped cantilevers with asymmetric pyramidal tips.

This paper deals with an application of 3D finite element analysis to the electrostatic interaction between (i) a commercial rectangular shaped cantilever (with an integrated anisotropic pyramidal tip) and a conductive sample, when a voltage difference is applied between them, and (ii) a focused ion beam (FIB) modified cantilever in order to realize a probe with reduced parasitic electrostatic force. The 3D modelling of their electrostatic deflection was realized by using multiphysics finite element analysis software and applied to the real geometry of the cantilevers and probes as used in conventional electric and Kelvin force microscopy to evaluate the contribution of the various part of a cantilever to the total force, and derive practical criteria to optimize the probe performances. We report also on the simulation of electrostatic shielding of nanometric features, in order to quantitatively evaluate an alternative way of reducing the systematic error caused by the cantilever-to-sample capacitive coupling. Finally, a quantitative comparison between the performances of rectangular and triangular cantilevers (part I of this work) is reported.