Sub-stoichiometric functionally graded titania fibres for water-splitting applications

The photo-electro-chemical (PEC) splitting of water requires semiconductor materials with a minimum energy gap of 1.23 eV along with conduction and valence bands overlapping the oxidation of H2O and reduction of H+ respectively. This work overcomes the limitations of stoichiometric titania by manufacturing fine scale fibres that exhibit a compositional gradient of oxygen vacancies across the fibre length. In such a fibre configuration the fibre end that is chemically reduced to a relatively small extent performs as the photoanode and the oxygen vacancies enhance the absorption of light. The fibre end that is reduced the most consists of Magnéli phases and exhibits metallic electrical conductivity that enhances the electron-hole separation. The structure and composition of the functionally graded fibres, which were manufactured through extrusion, pressureless sintering and carbo-thermal reduction, are studied using XRD and electron microscopy. Electrochemical impedance spectroscopy measurements were performed in a three-electrode electrochemical system and showed that the oxygen vacancies in the functionally graded fibres affect the flat band potential and have increased carrier density. The efficiency of the system was evaluated with PEC measurements that shows higher efficiency for the functionally graded fibres compared to homogeneous TiO2 or Magnéli phase fibres. The functionally graded and fine scale fibres have the potential to be used as an array of active fibres for water splitting applications.</p

Quantum fluctuations in one-dimensional arrays of condensates

The effects of quantum and thermal fluctuations upon the fringe structure predicted to be observable in the momentum distribution of coupled Bose-Einstein condensates are studied by the effective-potential method. For a double-well trap, the coherence factor recently introduced by Pitaevskii and Stringari [Phys. Rev. Lett. 87, 180402 (2001)] is calculated using the effective potential approach and is found in good agreement with their result. The calculations are extended to the case of a one-dimensional array of condensates, showing that quantum effects are essentially described through a simple renormalization of the energy scale in the classical analytical expression for the fringe structure. The consequences for the experimental observability are discussed.Comment: RevTeX, 4 pages, 5 eps figures (published version with updated references

Quantum thermodynamics of systems with anomalous dissipative coupling

The standard {\em system-plus-reservoir} approach used in the study of dissipative systems can be meaningfully generalized to a dissipative coupling involving the momentum, instead of the coordinate: the corresponding equation of motion differs from the Langevin equation, so this is called {\em anomalous} dissipation. It occurs for systems where such coupling can indeed be derived from the physical analysis of the degrees of freedom which can be treated as a dissipation bath. Starting from the influence functional corresponding to anomalous dissipation, it is shown how to derive the effective classical potential that gives the quantum thermal averages for the dissipative system in terms of classical-like calculations; the generalization to many degrees of freedom is given. The formalism is applied to a single particle in a double-well and to the discrete $\phi^4$ model. At variance with the standard case, the fluctuations of the coordinate are enhanced by anomalous dissipative coupling.Comment: 12 pages, 5 figures, to be published in Phys. Rev.

Sub-stoichiometric functionally graded titania fibres for water-splitting applications

The photo-electro-chemical (PEC) splitting of water requires semiconductor materials with a minimum energy gap of 1.23 eV along with conduction and valence bands overlapping the oxidation of H2O and reduction of H+ respectively. This work overcomes the limitations of stoichiometric titania by manufacturing fine scale fibres that exhibit a compositional gradient of oxygen vacancies across the fibre length. In such a fibre configuration the fibre end that is chemically reduced to a relatively small extent performs as the photoanode and the oxygen vacancies enhance the absorption of light. The fibre end that is reduced the most consists of Magnéli phases and exhibits metallic electrical conductivity that enhances the electron-hole separation. The structure and composition of the functionally graded fibres, which were manufactured through extrusion, pressureless sintering and carbo-thermal reduction, are studied using XRD and electron microscopy. Electrochemical impedance spectroscopy measurements were performed in a three-electrode electrochemical system and showed that the oxygen vacancies in the functionally graded fibres affect the flat band potential and have increased carrier density. The efficiency of the system was evaluated with PEC measurements that shows higher efficiency for the functionally graded fibres compared to homogeneous TiO2 or Magnéli phase fibres. The functionally graded and fine scale fibres have the potential to be used as an array of active fibres for water splitting applications.</p

Thermodynamics of the quantum easy-plane antiferromagnet on the triangular lattice

The classical XXZ triangular-lattice antiferromagnet (TAF) shows both an Ising and a BKT transition, related to the chirality and the in-plane spin components, respectively. In this paper the quantum effects on the thermodynamic quantities are evaluated by means of the pure-quantum self-consistent harmonic approximation (PQSCHA), that allows one to deal with any spin value through classical MC simulations. We report the internal energy, the specific heat, and the in-plane correlation length of the quantum XX0 TAF, for S=1/2, 1, 5/2. The quantum transition temperatures turn out to be smaller the smaller the spin, and agree with the few available theoretical and numerical estimates.Comment: 4 pages,3 postscript figure

Ultramicronized palmitoylethanolamide reduces viscerovisceral hyperalgesia in a rat model of endometriosis plus ureteral calculosis: role of mast cells.

The effects of ultramicronized palmitoylethanolamide were evaluated on pain behaviours and markers of mast cell (MC) activity in 'a rat model of endometriosis plus ureteral calculosis (ENDO+STONE)-induced viscerovisceral hyperalgesia (VVH). Female Sprague-Dawley rats that underwent surgical induction of endometriosis were randomly assigned to receive active (ultramicronized palmitoylethanolamide 10 mg·kg-1 ·d-1, orally) or placebo treatment for 25 days. At day 21, they underwent ureteral stone formation and were video-recorded till day 25 to evaluate ureteral and uterine pain behaviours. At autopsy (day 25), ureteral condition and number and diameter of endometrial cysts were evaluated. The following were then measured: number and percentage of degranulating MCs, number of vessels, chymase, nerve growth factor (NGF), vascular endothelial growth factor (VEGF), and Flk-1 (VEGF receptor) in cysts, and NGF in dorsal root ganglia (DRG). Ultramicronized palmitoylethanolamide-treated vs placebo-treated rats showed significantly lower number, duration and complexity of ureteral crises, shorter duration of uterine pain, and smaller cyst diameter (0.0001 < P < 0.004); a significantly higher percentage of expelled stones (P < 0.0001); significantly lower MC number (P<0.01), vessel number (P< 0.01), chymase (P< 0.05), NGF (P<0.05), VEGF (P< 0.01), and Flk-1 (P< 0.01) expression in cysts and NGF expression in DRG (P< 0.01). In all animals, the global duration of ureteral crises correlated linearly and directly with cyst diameter, MC number and chymase in cysts, and NGF in cysts and DRG (0.02 < P < 0.0002). Ultramicronized palmitoylethanolamide significantly reduces VVH from ENDO+STONE, probably by modulating MC expression/activity in cysts, thus reducing central sensitization due to noxious signals from endometriotic lesions. The results suggest potential utility of the compound for VVH in clinics

The two-dimensional quantum Heisenberg antiferromagnet: effective Hamiltonian approach to the thermodynamics

In this paper we present an extensive study of the thermodynamic properties of the two-dimensional quantum Heisenberg antiferromagnet on the square lattice; the problem is tackled by the pure-quantum self-consistent harmonic approximation, previously applied to quantum spin systems with easy-plane anisotropies, modeled to fit the peculiar features of an isotropic system. Internal energy, specific heat, correlation functions, staggered susceptibility, and correlation length are shown for different values of the spin, and compared with the available high-temperature expansion and quantum Monte Carlo results, as well as with the available experimental data.Comment: 14 pages, 13 Postscript figures embedded by psfig.sty; revisions: paper shortened, some parts moved in the appendices, 4 figures replaced by 2 only, minor errors correcte

Semiclassical approach to the thermodynamics of spin chains

Using the PQSCHA semiclassical method, we evaluate thermodynamic quantities of one-dimensional Heisenberg ferro- and antiferromagnets. Since the PQSCHA reduces their evaluation to classical-like calculations, we take advantage of Fisher's exact solution to get all results in an almost fully analytical way. Explicitly considered here are the specific heat, the correlations length and susceptibility. Good agreement with Monte Carlo simulations is found for S>1 antiferromagnets, showing that the relevance of the topological terms and of the Haldane gap is significant only for the lowest spin values and temperatures.Comment: 4 pages, 7 figure

Effect of tecovirimat on healing time and viral clearance by emulation of a target trial in patients hospitalized for mpox

Tecovirimat is a treatment option for severe mpox, although randomized clinical trials are ongoing. The aim of the study is to assess the effect of tecovirimat on healing time and the extent of viral clearance by target trial emulation using observational data. Clinical and virological data of patients hospitalized for mpox were collected. Samples from the upper respiratory tract (URT) were grouped in two time points: T1 (median 6 days from symptoms onset) and T2 (median 5 days from T1). Patients were followed-up until recovery. Average treatment effect (ATE) in patients untreated versus treated with tecovirimat was estimated on time to healing and variation in viral load in URT, using a weighted and cloning analysis. Among the 41 patients included, 19 completed a course of tecovirimat. The median time from symptoms onset to hospitalization and to drug-starting was 4 days and 10 days, respectively. No improvement in healing time in treated versus untreated was observed. No difference by treatment group in time to viral clearance was detected by ATE fitted in a subset of 13 patients after controlling for confounders. We found no evidence for a large effect of tecovirimat in shortening healing time and viral clearance. While awaiting the results of randomized studies, the use of tecovirimat should be restricted to the clinical trial setting