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

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

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

Possible Assessment of Calf Venous Pump Efficiency by Computational Fluid Dynamics Approach

Three-dimensional simulations of peripheral, deep venous flow during muscular exercise in limbs of healthy subjects and in those with venous dysfunction were carried out by a computational fluid-dynamics (CFD) approach using the STAR CCM + platform. The aim was to assess the effects of valvular incompetence on the venous calf pump efficiency. The model idealizes the lower limb circulation by a single artery, a capillary bed represented by a porous region and a single vein. The focus is on a segment of the circuit which mimics a typical deep vein at the level of the calf muscle, such as the right posterior tibial vein. Valves are idealized as ball valves, and periodic muscle contractions are given by imposing time-dependent boundary conditions to the calf segment wall. Flow measurements were performed in two cross-sections downstream and upstream of the calf pump. Model results demonstrate a reduced venous return for incompetent valves during calf exercise. Two different degrees of valvular incompetence are considered, by restricting the motion of one or both valves. Model results showed that only the proximal valve is critical, with a 30% reduction of venous return during calf exercise in case of valvular incompetence: the net flow volume ejected by the calf in central direction was 0.14 mL per working cycle, against 0.2 mL for simulated healthy limbs. This finding appeared to be consistent with a 25% reduction of the calf ejection fraction, experimentally observed in chronic venous disease limbs compared with healthy limbs

The Diet and Haemodialysis Dyad: Three Eras, Four Open Questions and Four Paradoxes. A Narrative Review, Towards a Personalized, Patient-Centered Approach

The history of dialysis and diet can be viewed as a series of battles waged against potential threats to patients’ lives. In the early years of dialysis, potassium was identified as “the killer”, and the lists patients were given of forbidden foods included most plant-derived nourishment. As soon as dialysis became more efficient and survival increased, hyperphosphatemia, was identified as the enemy, generating an even longer list of banned aliments. Conversely, the “third era” finds us combating protein-energy wasting. This review discusses four questions and four paradoxes, regarding the diet-dialysis dyad: are the “magic numbers” of nutritional requirements (calories: 30–35 kcal/kg; proteins > 1.2 g/kg) still valid? Are the guidelines based on the metabolic needs of patients on “conventional” thrice-weekly bicarbonate dialysis applicable to different dialysis schedules, including daily dialysis or haemodiafiltration? The quantity of phosphate and potassium contained in processed and preserved foods may be significantly different from those in untreated foods: what are we eating? Is malnutrition one condition or a combination of conditions? The paradoxes: obesity is associated with higher survival in dialysis, losing weight is associated with mortality, but high BMI is a contraindication for kidney transplantation; it is difficult to limit phosphate intake when a patient is on a high-protein diet, such as the ones usually prescribed on dialysis; low serum albumin is associated with low dialysis efficiency and reduced survival, but on haemodiafiltration, high efficiency is coupled with albumin losses; banning plant derived food may limit consumption of “vascular healthy” food in a vulnerable population. Tailored approaches and agreed practices are needed so that we can identify attainable goals and pursue them in our fragile haemodialysis populations