The Color and Stability of Maya Blue: TDDFT Calculations

Car-Parrinello structural optimizations of realistic models of the Maya Blue (MB) hybrid material are combined with TDDFT calculations of the electronic excitation spectra to identify the nature of the fundamental guest-host interactions leading to the unusual stability of this pigment. The comparison with the features of the experimental visible spectrum reveals that the main mode of interaction between the host solid (the palygorskite clay) and the guest molecule (the organic indigo dye) involves the coordination of the carbonyl group of the dye by Al3+ ions exposed at the edge of the palygorskite tunnels. Analogous Mg2+-dye interactions which do not strongly affect the MB visible spectrum can also be present. Thermal treatment used in the preparation of the pigment appears therefore essential to release some of the structural water molecules tightly bound to the Al3+ ions in the internal clay surface, thus leaving them available to coordinate the organic molecule. Moderate heating also favors the oxidation of indigo to dehydroindigo (DHI): the spectral features of the latter complex with Al3+ are in remarkable agreement with the experimental spectrum, thus confirming the substantial role of DHI in the properties of Maya Blue

Competition between water and hydrogen peroxide at Ti center in Titanium zeolites. An ab initio study

A combined Car 12Parrinello molecular dynamics blue moon sampling approach has been adopted to study the competitive attack of H2O and H2O2 at a tetracoordinated Titanium site in a Ti 12zeolite. The results indicate that, although the attack of water to form a trigonal bipyramidal center is thermodynamically more stable, the attack of hydrogen peroxide to form a similar adduct is kinetically favored. In both cases, solvent cooperation is effective in the formation of the adducts. The relevance of such a result in relation to the catalytic properties of Ti 12zeolites is discussed

TS-1 from First Principles

First principles Studies on periodic TS-1 models at Ti content corresponding to 1.35% and 2.7% in weight of TiO2 are presented. The problem of Ti preferential siting is addressed by using realistic models corresponding to the TS-1 unit cell [TiSi95O192] and adopting for the first time a periodic DFT approach, thus providing an energy scale for Ti in the different crystallographic sites in nondefective TS-1. The structure with Ti in site T3 is the most stable, followed by T4 (+0.3 kcal/mol); the less stable structure, corresponding to Ti in T1, is 5.6 kcal/mol higher in energy. The work has been extended to investigate models with two Ti's per unit cell [Ti2Si94O192] (2.7%). The possible existence of Ti-O-Ti bridges, formed by two corner-sharing TiO4 tetrahedra, is discussed. By using Cluster models cut from the optimized periodic DFT structures, both vibrational (DFT) and electronic excitation spectra (TDDFT) have been calculated and favorably compared with the experimental data available on TS-1. Interesting features emerged from excitation spectra: (i) Isolated tetrahedral Ti sites show a Beer-Lambert behavior, with absorption intensity proportional to concentration. Such a behavior is gradually lost when two Ti's occupy sites close to each other. (ii) The UV-vis absorption in the 200-250 nm region can be associated with transitions from Occupied states delocalized on the framework oxygens to empty d states localized on Ti. Such extended-states-to-local-states transitions may help the interpretation of the photovoltaic activity recently detected in Ti zeolites

Gone with the waves: the role of sea currents as key dispersal mechanism for Mediterranean coastal and inland plant species

Thalassochory, the dispersal of propagules through marine currents, is a key long-distance dispersal (LDD) mechanism with implications for global biogeography and particularly for island colonization. The propagules of coastal plant species are generally assumed to be better adapted for sea dispersal than those of inland plants, but this hypothesis remains largely untested. We conducted experiments on four genera (Juniperus, Daucus, Ferula, and Pancratium) and compared traits among nine species with different habitats and distributions. Our results showed that Juniperus spp. and P. maritimum have strong thalassochorous potential within the Mediterranean Basin. Interestingly, we did not find a clear association on the thalassochorous potential of coastal versus inland species within all the tested genera, apart from P. maritimum compared with the endemic inland P. illyricum. These findings suggest that thalassochory may be a more common dispersal mechanism than previously assumed. The apparently weak link of dispersal syndrome with species ecology broadens the possibility of dispersal by the sea also for inland plants, although considered to be poorly salt-tolerant. Moreover, our results reveal significant differences in sea dispersal between endemic and widespread species, but do not rule out an important role of thalassochory in shaping the distribution patterns of archipelago endemic flora. The presented method is largely replicable and could be used for further studies with a larger set of species to better delineate trends of sea dispersal syndrome among species with different ecology or dispersal traits

Water in acid boralites: Hydration effects on framework B sites

Properties and behavior of protonated boron-containing zeolites at different hydration degree have been investigated by means of periodic DFT approaches. Geometry optimization and room-temperature Car-Parrinello molecular dynamics results, in line with experimental findings, indicate that the BO3-bound silanolic acid site typical of dry boralites should convert to a solvated H3O+ hydrogen bonded to tetrahedral BO4 at moderate water content. By increasing the water loading, the tetrahedral structure of the B site is stabilized and the physicochemical properties of the water molecules solvating the acid proton gradually approach the liquid-phase ones. A relevant role of structural and vibrational properties of the zeolite framework in the water-induced trigonal-to-tetrahedral transition at the B site is highlighted by simulation results

"Hot" Surface Activation of Molecular Complexes: Insight from Modeling Studies

Rock-and-roll over hot floors: Theoretical modeling of the first activation stages of a Cu complex on top of a heated surface (750 K) revealed two mobility regimes, a slow bump-and-rock diffusion over the surface and a fast roll-and-go motion accompanied by significant temperature-induced bond oscillations. This study enables a deeper insight into "hot" surface molecular activation processes.Tanz auf dem Vulkan: Das Modellieren der ersten Aktivierungsstufen eines Cu-Komplexes auf einer beheizten Oberfl\ue4che (750\u2005K) enth\ufcllte zwei Bewegungsarten: eine langsame Diffusion durch \u201eAnsto fen und Taumeln\u201c und eine schnelle Rollbewegung, die mit deutlichen temperaturinduzierten Bindungsoszillationen einhergeht. Diese Befunde geben einen Einblick in die Prozesse bei der Aktivierung durch \u201ehei fe\u201c Oberfl\ue4chen

Hydroxytyrosol but not resveratrol ingestion induced an acute increment of post exercise blood flow in brachial artery

The aim of this study was to test if previous ingestion of compounds containing resveratrol or hydroxytyrosol, followed by an exhausting hand grip exercise, could induce an acute post-exercise increase in brachial blood flow. Six healthy subjects (three males and three females, 35 ± 7 years), 60 minutes after ingestion of a capsule containing 200 mg of resveratrol or 30 ml of extra virgin olive oil enriched with tyrosol, oleuropein and hydroxytyrosol, performed a hand grip exercise equal to half of their maximum strength until they were no longer able to express the same force (2-day interval between tests). The nonparametric Wilcoxon signed rank test was used for statistical evaluations. Brachial artery blood flow (Fba) and both blood velocity (Vba) and artery diameter (Dba) were assessed immediately after exercise cessation by means of colour Doppler ultrasound. After ingestion of the oil mixture the post-exercise value of Fba median was 2.4 times higher than that after ingestion of the resveratrol compound (P = 0.03), and also the Vba median concerning the hydroxytyrosol was 1.9 times higher than that of the resveratrol (P = 0.03). Both functional foods did not lead to a significant difference in the Dba medians. These results indicate that hydroxytyrosol, but not resveratrol, may be an effective adjuvant of recreational or agonistic, long-lasting sports performances, thanks to the powerful blood flow increment which can be obtained as soon as one hour from its oral intake

Landslide run-out simulations with depth-averaged models and integration with 3D impact analysis using the Material Point Method

Landslides pose a significant threat to human safety and the well-being of com- munities, making them one of the most challenging natural phenomena. Their potential for catastrophic consequences, both in terms of human lives and economic impact, is a major con- cern. Additionally, their inherent unpredictability adds to the complexity of managing the risks associated with landslides. It is crucial to continuously monitor areas susceptible to landslides. In situ detection systems like piezometers and strain gauges play a vital role in accurately mon- itoring internal pressures and surface movements in the targeted areas. Simultaneously, satel- lite surveys contribute by offering detailed topographic and elevation data for the study area. However, relying solely on empirical monitoring is insufficient for ensuring effective manage- ment of hazardous situations, especially in terms of preventive measures. This study provides advanced simulations of mudflows and fast landslides using particle depth-averaged methods, specifically employing the Material Point Method adapted for shallow water (Depth Averaged Material Point Method). The numerical method has been parallelized and validated through benchmark tests and real-world cases. Furthermore, the investigation extends to coupling the depth-averaged formulation with a three-dimensional one in order to have a detailed description of the impact phase of the sliding material on barriers and membranes. The multidimensional approach and its validation on real cases provide a robust foundation for a more profound and accurate understanding of the behavior of mudflows and fast landslides

Predicting the potential current and future distribution of the endangered endemic vascular plant primula boveana decne. ex duby in Egypt

Knowledge about population attributes, current geographic distribution, and changes over predicted climate change for many threatened endemic vascular plants is particularly limited in arid mountain environments. Primula boveana is one of the rarest and threatened plants worldwide, surviving exclusively in Saint Catherine Protectorate in the Sinaic biogeographic subsector of Egypt. This study aimed to define the current state of P. boveana populations, predict its current potential distribution, and use the best-model outputs to guide in field sampling and to forecast its future distribution under two climate change scenarios. The MaxEnt algorithm was used by relating 10 occurrence-points with different environmental predictors (27 bioclimatic, 3 topographic, and 8 edaphic factors). At the current knowledge level, the population size of P. boveana consists of 796 individuals, including 137 matures, distributed in only 250 m2. The Canonical Correlation Analysis (CCorA) displayed that population attributes (density, cover, size index, and plant vigor) were positively correlated with elevation, precipitation, and pH. Based on the best-fitting model, most predicted suitable central sites (69 km2) of P. boveana were located in the cool shaded high-elevated middle northern part of St. Catherine. Elevation, precipitation, temperature, and soil pH were the key contributors to P. boveana distribution in Egypt. After field trips in suitable predicted sites, we confirmed five extinct localities where P. boveana has been previously recorded and no new population was found. The projected map showed an upward range shift through the contraction of sites between 1800 and 2000 m and expansion towards high elevation (above 2000 m) at the southern parts of the St. Catherine area. To conserve P. boveana, it is recommended to initiate in situ conservation through reinforcement and reintroduction actions