Investigation of HNCO isomers formation in ice mantles by UV and thermal processing: an experimental approach

Current gas phase models do not account for the abundances of HNCO isomers detected in various environments, suggesting a formation in icy grain mantles. We attempted to study a formation channel of HNCO and its possible isomers by vacuum-UV photoprocessing of interstellar ice analogues containing H$_2$O, NH$_3$, CO, HCN, CH$_3$OH, CH$_4$, and N$_2$ followed by warm-up, under astrophysically relevant conditions. Only the H$_2$O:NH$_3$:CO and H$_2$O:HCN ice mixtures led to the production of HNCO species. The possible isomerization of HNCO to its higher energy tautomers following irradiation or due to ice warm-up has been scrutinized. The photochemistry and thermal chemistry of H$_2$O:NH$_3$:CO and H$_2$O:HCN ices was simulated using the Interstellar Astrochemistry Chamber (ISAC), a state-of-the-art ultra-high-vacuum setup. The ice was monitored in situ by Fourier transform mid-infrared spectroscopy in transmittance. A quadrupole mass spectrometer (QMS) detected the desorption of the molecules in the gas phase. UV-photoprocessing of H$_2$O:NH$_3$:CO/H$_2$O:HCN ices lead to the formation of OCN$^-$ as main product in the solid state and a minor amount of HNCO. The second isomer HOCN has been tentatively identified. Despite its low efficiency, the formation of HNCO and the HOCN isomers by UV-photoprocessing of realistic simulated ice mantles, might explain the observed abundances of these species in PDRs, hot cores, and dark clouds

Data-driven reconstruction of chaotic dynamical equations: the H\'enon-Heiles type system

In this study, the classical two-dimensional potential $V_N=\frac{1}{2}\,m\,\omega^2\,r^2 + \frac{1}{N}\,r^N\,\sin(N\,\theta)$, $N \in {\mathbb Z}^+$, is considered. At $N=1,2$, the system is superintegrable and integrable, respectively, whereas for $N>2$ it exhibits a richer chaotic dynamics. For instance, at $N=3$ it coincides with the H\'enon-Heiles system. The periodic, quasi-periodic and chaotic motions are systematically characterized employing time series, Poincar\'e sections, symmetry lines and the largest Lyapunov exponent as a function of the energy $E$ and the parameter $N$. Concrete results for the lowest cases $N=3,4$ are presented in complete detail. This model is used as a benchmark system to estimate the accuracy of the Sparse Identification of Nonlinear Dynamical Systems (SINDy) method, a data-driven algorithm which reconstructs the underlying governing dynamical equations. We pay special attention at the transition from regular motion to chaos and how this influences the precision of the algorithm. In particular, it is shown that SINDy is a robust and stable tool possessing the ability to generate non-trivial approximate analytical expressions for periodic trajectories as well

Fog interception by Ball moss (<i>Tillandsia recurvata</i>)

Interception losses are a major influence in the water yield of vegetated areas. For most storms, rain interception results in less water reaching the ground. However, fog interception can increase the overall water storage capacity of the vegetation and once the storage is exceeded, fog drip is a common hydrological input. Fog interception is disregarded in water budgets of semiarid regions, but for some plant communities, it could be a mechanism offsetting evaporation losses. <i>Tillandsia recurvata</i> is a cosmopolitan epiphyte adapted to arid habitats where fog may be an important water source. Therefore, the interception storage capacity by <i>T. recurvata</i> was measured in controlled conditions and applying simulated rain or fog. Juvenile, vegetative specimens were used to determine the potential upperbound storage capacities. The storage capacity was proportional to dry weight mass. Interception storage capacity (<i>C</i>_min) was 0.19 and 0.56 mm for rainfall and fog respectively. The coefficients obtained in the laboratory were used together with biomass measurements for <i>T. recurvata</i> in a xeric scrub to calculate the depth of water intercepted by rain. <i>T. recurvata</i> contributed 20 % to the rain interception capacity of their shrub hosts: <i>Acacia farnesiana</i> and <i>Prosopis laevigata</i> and; also potentially intercepted 4.8 % of the annual rainfall. Nocturnal stomatic opening in <i>T. recurvata</i> is not only relevant for CO₂ but for water vapor, as suggested by the higher weight change of specimens wetted with fog for 1 h at dark in comparison to those wetted during daylight (543 ± 77 vs. 325 ± 56 mg, <i>p</i> = 0.048). The storage capacity of <i>T. recurvata</i> leaf surfaces could increase the amount of water available for evaporation, but as this species colonise montane forests, the effect could be negative on water recharge, because potential storage capacity is very high, in the laboratory experiments it took up to 12 h at a rate of 0.26 l h⁻¹ to reach saturation conditions when fog was applied

Assessing Value-based Health Care Delivery for Hemodialysis

Rationale, aims and objectives Disparities in haemodialysis outcomes among centres have been well-documented. Besides, attempts to assess haemodialysis results have been based on non-comprehensive methodologies. This study aimed to develop a comprehensive methodology for assessing haemodialysis centres, based on the value of health care. The value of health care is defined as the patient benefit from a specific medical intervention per monetary unit invested (Value = Patient Benefit/Cost). This study assessed the value of health care and ranked different haemodialysis centres. Method A nephrology quality management group identified the criteria for the assess- ment. An expert group composed of stakeholders (patients, clinicians and managers) agreed on the weighting of each variable, considering values and preferences. Multi-criteria methodology was used to analyse the data. Four criteria and their weights were identified: evidence-based clinical performance measures = 43 points; yearly mortality = 27 points; patient satisfaction = 13 points; and health-related quality of life = 17 points (100-point scale). Evidence-based clinical performance measures included five sub-criteria, with respective weights, including: dialysis adequacy; haemoglobin concentration; mineral and bone disorders; type of vascular access; and hospitalization rate. The patient benefit was determined from co-morbidity–adjusted results and corresponding weights. The cost of each centre was calculated as the average amount expended per patient per year. Results The study was conducted in five centres (1–5). After adjusting for co-morbidity, value of health care was calculated, and the centres were ranked. A multi-way sensitivity analysis that considered different weights (10–60% changes) and costs (changes of 10% in direct and 30% in allocated costs) showed that the methodology was robust. The rankings: 4-5-3-2-1 and 4-3-5-2-1 were observed in 62.21% and 21.55%, respectively, of simula- tions, when weights were varied by 60%. Conclusions Value assessments may integrate divergent stakeholder perceptions, create a context for improvement and aid in policy-making decisions

Influence of excesses of volatile elements on structure and composition of solution derived lead-free (Bi0.50Na0.50)1xBaxTiO3 thin films

The preparation of (Bi0.50Na0.50)1−xBaxTiO3 films requires a compositional/structural control, as they determine the functionality of these materials. We report a systematic compositional and structural analysis on (Bi0.50Na0.50)1−xBaxTiO3 films fabricated by chemical solution deposition. The effects of incorporating Na(I) and Bi(III) excesses are analyzed through the comparison of the compositional depth profiles of stoichiometric films (BNBT) and films containing excesses (BNBTxs). Heterogeneous compositional profiles with larger bismuth content close to the substrate and thicker film-substrate interfaces are observed in BNBTxs, unlike stoichiometric films, which show atomic concentrations that correspond to the nominal composition of the precursor solution. Excesses induce structural differences in depth, observing a shift of the region of coexistence of rhombohedral and tetragonal phases (morphotropic phase boundary) toward higher x values and the formation of thick film-substrate interfaces. In contrast, stoichiometric films have homogeneous compositional and structural profiles with the MPB placed close to that described for bulk ceramics.This work was financed by Spanish Project MAT2013-40489-P. D. Pérez-Mezcua acknowledges the financial support of the FPU Spanish program (AP2012-0639). A portion of this research was carried out at the Stanford Synchrotron Radiation Lightsource, a national user facility operated by Stanford University. D. Chateigner acknowledges the Conseil Régional de Basse Normandie for its partial financial of the four-circles X-ray diffractometer.Peer reviewe

Soft X-Ray Irradiation of H2S Ice and the Presence of S2 in Comets

Little is known about the effects of X-rays in interstellar ices. To understand the sulfur depletion in dense clouds and the presence of S2 in comets, we simulated experimentally the soft X-ray processing (0.3 keV) of H2 Si ce for the first time. Experiments were performed under ultrahigh vacuum conditions at 8 K using infrared and quadrupole mass spectrometry to monitor the solid and gas phases, respectively. A UV irradiation experiment using a similar dose was made for comparison. After X-ray irradiation, an infrared absorption appears near 4.0 μm which is attributed to H2S2 formation in the ice. This identification is also supported by the desorption at 133 K of m/z 66, 65, 64, corresponding to the mass fragments of H2S2 .T he H 2S2 species is expected to be present in interstellar and cometary ices that were processed by X-rays. Further irradiation leads to dissociation of this molecule forming S2 and larger S-molecules up to S8, which may explain the depletion of sulfur in dense clouds. CS2 was so far the parent molecule proposed for S2 formation in comets. But the abundance of H2S2, formed by irradiation of pure H2 So r H 2 Si n an H 2O–ice matrix, should be larger than that of CS2 in the ice, the latter requiring a carbon source for its formation. Based on our experimental results, we propose that S2 in comets could be formed by dissociation of H2S2 in the ice

Q switching and mode locking pulse generation from an all-fiber ring laser by intermodal acousto-optic bandpass modulation

Q-switched and mode-locked (QML) pulse generation from an all-fiber ring laser based on intermodal acousto-optic bandpass modulation is reported. The modulator relies on full-acousto-optic mode re-coupling cycle induced by a standing flexural acoustic wave, with a transmission response that is controlled by amplitude modulation of the acoustic wave signal. The Q factor of the cavity is controlled by a rectangular pulse wave with variable frequency and duty cycle, whereas mode locking is achieved by amplitude modulation derived from a standing flexural acoustic wave. The best QML pulses were obtained at 0.5 kHz repetition rate, with a pump power of 549.2 mW, at the optical wavelength of 1568.2 nm. A maximum overall energy of 2.14 µJ at an average output power of 1.07 mW was achieved, corresponding to a burst of mode-locked sub-pulses of 100 ps pulse duration within a QML envelope of 3.5 µs