Effect of the surface charge discretization on electric double layers. A Monte Carlo simulation study

The structure of the electric double layer in contact with discrete and continuously charged planar surfaces is studied within the framework of the primitive model through Monte Carlo simulations. Three different discretization models are considered together with the case of uniform distribution. The effect of discreteness is analyzed in terms of charge density profiles. For point surface groups,a complete equivalence with the situation of uniformly distributed charge is found if profiles are exclusively analyzed as a function of the distance to the charged surface. However, some differences are observed moving parallel to the surface. Significant discrepancies with approaches that do not account for discreteness are reported if charge sites of finite size placed on the surface are considered

Surface nanostructuring of TiO2 thin films by high energy ion irradiation

The effects of a high ion dose irradiation on TiO2 thin films under different conditions of temperature and ion nature are discussed. We have shown that anatase TiO2 thin films irradiated with N+ ions at room temperature develop a typical microstructure with mounds and voids open to the surface whereas irradiations at 700 K generate a surface pattern of well-ordered nanorods aligned with the ion beam. The formation of these patterns is caused by the simultaneous effect of ion irradiation near the film surface and a film temperature favoring the structural mobilization of the defective network of the material. To explain these phenomena, a qualitative model has been proposed and further tested by irradiating the TiO2 thin films with F+ and S+ ions under different conditions. The obtained results demonstrate that ion irradiation techniques enable the formation of tilted nanorod surface patterns with lengths of about 100 nm on anatase TiO2 thin films. © 2010 The American Physical Society.Peer Reviewe

Parkinsonian motor impairment predicts personality domains related to genetic risk and treatment outcomes in schizophrenia

Identifying endophenotypes of schizophrenia is of critical importance and has profound implications on clinical practice. Here we propose an innovative approach to clarify the mechanims through which temperament and character deviance relates to risk for schizophrenia and predict long-term treatment outcomes. We recruited 61 antipsychotic naïve subjects with chronic schizophrenia, 99 unaffected relatives, and 68 healthy controls from rural communities in the Central Andes. Diagnosis was ascertained with the Schedules of Clinical Assessment in Neuropsychiatry; parkinsonian motor impairment was measured with the Unified Parkinson’s Disease Rating Scale; mesencephalic parenchyma was evaluated with transcranial ultrasound; and personality traits were assessed using the Temperament and Character Inventory. Ten-year outcome data was available for ~40% of the index cases. Patients with schizophrenia had higher harm avoidance and self-transcendence (ST), and lower reward dependence (RD), cooperativeness (CO), and self-directedness (SD). Unaffected relatives had higher ST and lower CO and SD. Parkinsonism reliably predicted RD, CO, and SD after correcting for age and sex. The average duration of untreated psychosis (DUP) was over 5 years. Further, SD was anticorrelated with DUP and antipsychotic dosing at follow-up. Baseline DUP was related to antipsychotic dose-years. Further, ‘explosive/borderline’, ‘methodical/obsessive’, and ‘disorganized/schizotypal’ personality profiles were associated with increased risk of schizophrenia. Parkinsonism predicts core personality features and treatment outcomes in schizophrenia. Our study suggests that RD, CO, and SD are endophenotypes of the disease that may, in part, be mediated by dopaminergic function. Further, SD is an important determinant of treatment course and outcome

Low dose electron tomography of novel nanocomposites for additive manufacturing

This is an open access article under the CC BY-NC-ND licenseThe development of new nanocomposites with added functionalities for Additive Manufacturing (AM) requires of a deep understanding of the 3D distribution of the selected nano-additives within the polymeric matrix, in order to optimize their performance. For this, electron tomography (ET) is an outstanding analysis technique that requires the material to withstand the electron exposure needed for the acquisition of several tens of images, becoming challenging for beam-sensitive materials. In this work, we analyse the parameters involved in the successful analysis by low dose ET of nanocomposites based in acrylic resins for stereolithography (SLA). Needleshape electron-transparent specimens have been fabricated by focused ion beam (FIB), minimizing surface damage due to the high energy Ga+ ions. Microscope settings for tuning the electron dose applied during the ET analysis of these nanoneedles are discussed. A phenomenological study of the effect of increasing the electron dose in the scanning transmission electron microscopy (STEM) analysis of the material has been carried out, showing that ET can be effectively performed at low electron doses. Two case studies are presented, to illustrate the relevance of these analyses in the development of nanocomposites with added functionalities. Our results have revealed the crucial role of the dose rate and of inaccuracies in the calculation of critical electron doses for the design of ET experiments.Junta de Andalucía 00955Universidad de Cádiz PR2022-00

Assessing the Impact of Different Measurement Time Intervals on Observed Long-Term Wind Speed Trends

During the last two decades climate studies have reported a tendency toward a decline in measured near-surface wind speed in some regions of Europe, North America, Asia and Australia. This weakening in observed wind speed has been recently termed >global stilling>, showing a worldwide average trend of -0.140 m s -1 dec -1 during last 50-years. The precise cause of the >global stilling> remains largely uncertain and has been hypothetically attributed to several factors, mainly related to: (i) an increasing surface roughness (i.e. forest growth, land use changes, and urbanization); (ii) a slowdown in large-scale atmospheric circulation; (iii) instrumental drifts and technological improvements, maintenance, and shifts in measurements sites and calibration issues; (iv) sunlight dimming due to air pollution; and (v) astronomical changes. This study proposed a novel investigation aimed at analyzing how different measurement time intervals used to calculate a wind speed series can affect the sign and magnitude of long-term wind speed trends. For instance, National Weather Services across the globe estimate daily average wind speed using different time intervals and formulae that may affect the trend results. Here we analyzed near-surface wind speed trends recorded at 19 land-based stations across Spain comparing monthly mean wind speed series obtained from: (a) daily mean wind speed data averaged from standard 10-min mean observations at 0000, 0700, 1300 and 1800 UTC; and (b) average wind speed of 24 hourly measurements (i.e., wind run measurements) from 0000 to 2400 UTC. As a complementary analysis, in this study we also quantified the impact of anemometer drift (i.e. bearing malfunction) by presenting preliminary results (i.e. 11 months of paired measurements) from a comparison of one new anemometer sensor against one malfunctioned anemometer sensor due to old bearings.We would like to thank the AEMET for supplying wind speed data. C. A-M. received a postdoctoral fellowship # JCI-2011-10263. Research supported by projects CGL2011-27574-C02-02, CGL2011-27536/HID and CGL2011-29263-C02-01 financed by the Spanish Commission of Science and Technology.Peer Reviewe

Modification of the mechanical properties of core-shell liquid gallium nanoparticles by thermal oxidation at low temperature

Gallium nanoparticles (Ga NPs) are attracting increasing attention because of their appealing physical-chemical properties. In particular, their mechanical properties play a key role in the implementation of these core-shell structures on certain applications, such as soft and stretchable electronics. Thus, efforts are being addressed to modulate them mainly by chemical means. In contrast, this study investigates how the mechanical properties of the outer gallium thin oxide shell change when its thickness is increased through a thermal oxidation strategy. Specifically, as-deposited Ga NPs, as well as those subjected to thermal oxidation at 300 °C for three different times, are studied by performing single-particle indentations by atomic force microscopy over a wide range of NP radius. This analysis helps to confirm that the Reissner's thin-shell model for small deformations within the elastic regime is obeyed. From these data, the dependence of the shell stiffness and the Young's modulus of the gallium oxide on the thermal treatment is obtained. It is found that the shell stiffness increases with the annealing time, even by a factor of 50 under prolonged thermal oxidation, while the gallium oxide Young's modulus, close to 30 GPa, does not change significantlyThis research was supported by Spanish MINECO (Grants No. MAT2017-85089-C2-1R, CTQ2017-84309-C2-2-R, PID2019-106339GB-I00, PID2020-113142RB-C21) and the TRANSNANOAVANSENS program (Grant No.S2018/NMT-4349) from the Comunidad de Madrid and Junta de Andalucía (Research group INNANOMAT, ref. TEP-946). Co-funding from UE was also acknowledged. A.R.C. acknowledges Ramón y Cajal program (under Contract No. RYC-2015-18047). S.C.G and M.d.l.M. acknowledge Juan de la Cierva en Formación programmes (references FJC2019-041616-I and IJCI-2017-31507, respectively). F.J.P. was thankful for financial support by A.E. Consejo Superior de Investigaciones Científicas (under Grant No. CSIC-2019AEP150). TEM measurements were carried out at DME-SC-ICyT-UCA/ICTS-ELECM

Surface nanostructuring of TiO2 thin films by high energy ion irradiation

The effects of a high ion dose irradiation on TiO2 thin films under different conditions of temperature and ion nature are discussed. We have shown that anatase TiO2 thin films irradiated with N+ ions at room temperature develop a typical microstructure with mounds and voids open to the surface whereas irradiations at 700 K generate a surface pattern of well-ordered nanorods aligned with the ion beam. The formation of these patterns is caused by the simultaneous effect of ion irradiation near the film surface and a film temperature favoring the structural mobilization of the defective network of the material. To explain these phenomena, a qualitative model has been proposed and further tested by irradiating the TiO2 thin films with F+ and S+ ions under different conditions. The obtained results demonstrate that ion irradiation techniques enable the formation of tilted nanorod surface patterns with lengths of about 100 nm on anatase TiO2 thin films.Ministerio de Ciencia e Innovación MAT 2007-65764, 2010-CSD2008-00023, 200960I132Junta de Andalucía TEP2275, P07-FQM-0329

CVD synthesis of carbon spheres using NiFe-LDHs as catalytic precursors: structural, electrochemical and magnetoresistive properties

The gram-scale synthesis of carbon spheres with a diameter of ca. 740 nm has been achieved by means of a chemical vapour deposition method using NiFe-layered double hydroxides as a solid catalytic precursor. The presence of the catalyst (FeNi3) allows controlling the final size distribution, resulting in a monodisperse sample. Their structural properties exhibited a high degree of graphitization according to their ID/IG ratio. In addition, their morphological features were unveiled by FIB-SEM and HRTEM, showing that they are formed by solid inner cores, and presenting labile chain-like structures due to accretion procedures. The solution and posterior sonication of the samples in toluene gave rise to the well-defined isolated spheres. The textural and electrochemical properties of the spheres have been tested showing non-mesoporous structures with a good behaviour as electrode materials for supercapacitors due to the presence of redox functionalities on their surface. Finally, magneto-transport measurements have been carried out, demonstrating semiconductor behaviour, as well as a positive magnetoresistance effect (ca. 72%) for the lowest studied temperature (2 K)

Induced damage during STEM-EELS analyses on acrylic-based materials for Stereolithography

(Scanning) transmission electron microscopy, (S)TEM, offers a powerful characterization tool based on electron-matter interactions, highly valuable in materials science. However, the possible electron beam induced damage during (S)TEM measurements hinders the analysis of soft materials, such as acrylic resins. Importantly, acrylic resins offer an appealing playground for the development of novel composites with customized properties and convenient processing capabilities for 3D-printing technologies, including Stereolithography (SLA). There are several factors preventing the optimal performance of TEM measurements applied to acrylic resins, among which we focus on the quality of the analyzed specimen (i.e., compromise between thickness and robustness, to achieve electron transparency while keeping the material integrity), particularly challenging when working with soft materials; the electrostatic charging/discharging effects, resulting in sample drift and related noise/artefacts; and the radiolysis and knock-on electron-induced damage, which directly degrade the material under study. We explore and compare different methodologies to obtain resin specimens suitable for (S)TEM analysis, employed for the subsequent study of the electron–beam damage induced during STEM-EELS measurements. Furthermore, we propose likely underlying mechanisms explaining the acrylic resin degradation based on the different EELS monitored signals. On one hand, we assess the evolution of the carbon and oxygen content, as well as the material thinning as a function of the accumulated electron dose. On the other hand, we extract meaningful information from the spectral shape of carbon and oxygen K-edges upon increasing electron doses, unraveling likely degradation pathways. The earned understanding on the electron-beam induced damage and the determination of critical doses provide a useful framework for the implementation of (S)TEM techniques as useful tools to help in the smart engineering of acrylic-based composites for SLA.DME-SC-ICyT-ELECMI-UCAUnión Europea - Junta de Andalucía - INNANOMAT TEP94