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

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

Energy Transfer from Magnetic Iron Oxide Nanoparticles: Implications for Magnetic Hyperthermia

Magnetic iron oxide nanoparticles (IONPs) have gained momentum in the field of biomedical applications. They can be remotely heated via alternating magnetic fields, and such heat can be transferred from the IONPs to the local environment. However, the microscopic mechanism of heat transfer is still debated. By X-ray total scattering experiments and first-principles simulations, we show how such heat transfer can occur. After establishing structural and microstructural properties of the maghemite phase of the IONPs, we built a maghemite model functionalized with aminoalkoxysilane, a molecule used to anchor (bio)molecules to oxide surfaces. By a linear response theory approach, we reveal that a resonance mechanism is responsible for the heat transfer from the IONPs to the surroundings. Heat transfer occurs not only via covalent linkages with the IONP but also through the solvent hydrogen-bond network. This result may pave the way to exploit the directional control of the heat flow from the IONPs to the anchored molecules─i.e., antibiotics, therapeutics, and enzymes─for their activation or release in a broader range of medical and industrial applications

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

Prescribing Hemodialysis or Hemodiafiltration: When One Size Does Not Fit All the Proposal of a Personalized Approach Based on Comorbidity and Nutritional Status

There is no simple way to prescribe hemodialysis. Changes in the dialysis population, improvements in dialysis techniques, and different attitudes towards the initiation of dialysis have influenced treatment goals and, consequently, dialysis prescription. However, in clinical practice prescription of dialysis still often follows a “one size fits all” rule, and there is no agreed distinction between treatment goals for the younger, lower-risk population, and for older, high comorbidity patients. In the younger dialysis population, efficiency is our main goal, as assessed by the demonstrated close relationship between depuration (tested by kinetic adequacy) and survival. In the ageing dialysis population, tolerance is probably a better objective: “good dialysis” should allow the patient to attain a stable metabolic balance with minimal dialysis-related morbidity. We would like therefore to open the discussion on a personalized approach to dialysis prescription, focused on efficiency in younger patients and on tolerance in older ones, based on life expectancy, comorbidity, residual kidney function, and nutritional status, with particular attention placed on elderly, high-comorbidity populations, such as the ones presently treated in most European centers. Prescription of dialysis includes reaching decisions on the following elements: dialysis modality (hemodialysis (HD) or hemodiafiltration (HDF)); type of membrane (permeability, surface); and the frequency and duration of sessions. Blood and dialysate flow, anticoagulation, and reinfusion (in HDF) are also briefly discussed. The approach described in this concept paper was developed considering the following items: nutritional markers and integrated scores (albumin, pre-albumin, cholesterol; body size, Body Mass Index (BMI), Malnutrition Inflammation Score (MIS), and Subjective Global Assessment (SGA)); life expectancy (age, comorbidity (Charlson Index), and dialysis vintage); kinetic goals (Kt/V, normalized protein catabolic rate (n-PCR), calcium phosphate, parathyroid hormone (PTH), beta-2 microglobulin); technical aspects including vascular access (fistula versus catheter, degree of functionality); residual kidney function and weight gain; and dialysis tolerance (intradialytic hypotension, post-dialysis fatigue, and subjective evaluation of the effect of dialysis on quality of life). In the era of personalized medicine, we hope the approach described in this concept paper, which requires validation but has the merit of providing innovation, may be a first step towards raising attention on this issue and will be of help in guiding dialysis choices that exploit the extraordinary potential of the present dialysis “menu”

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