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Composite likelihood inference has gained much popularity thanks to its computational manageability and its theoretical properties. Unfortunately, performing composite likelihood ratio tests is inconvenient because of their awkward asymptotic distribution. There are many proposals for adjusting composite likelihood ratio tests in order to recover an asymptotic chi-square distribution, but they all depend on the sensitivity and variability matrices. The same is true for Wald-type and score-type counterparts. In realistic applications, sensitivity and variability matrices usually need to be estimated, but there are no comparisons of the performance of composite likelihood-based statistics in such an instance. A comparison of the accuracy of inference based on the statistics considering two methods typically employed for estimation of sensitivity and variability matrices, namely an empirical method that exploits independent observations, and Monte Carlo simulation, is performed. The results in two examples involving the pairwise likelihood show that a very large number of independent observations should be available in order to obtain accurate coverages using empirical estimation, while limited simulation from the full model provides accurate results regardless of the availability of independent observations. This suggests the latter as a default choice, whenever simulation from the model is possible. [ABSTRACT FROM AUTHOR]

We have used energy-filtered photoemission electron microscopy (PEEM) at the photoemission threshold to carry out a microscopic scale characterization of the surface charge and domain structure of the (001) surface in BaTiO3. Signatures of ferroelectric and ferroelastic domains, and tweed, dominate the surface structure of BaTiO3 at room temperature. The surface ferroic signatures are maintained on heating to temperature (~550 K), well above the transition temperature (393 K). This surface proximity effect provides the mechanism for memory of the bulk ferroelectric domain arrangement up to 150 K above TC and thus can be considered as a robust fingerprint of the ferroelectric state near the surface. Self-reversal of polarization is observed for the tweed below TC and for the surface domains above TC. Annealing at higher temperature triggers the dynamic tweed which in turn allows a full reorganization of the ferroic domain configuration. [ABSTRACT FROM AUTHOR]

We have used energy-filtered photoemission electron microscopy (PEEM) at the photoemission threshold to carry out a microscopic scale characterization of the surface charge and domain structure of the (001) surface in BaTiO3. Signatures of ferroelectric and ferroelastic domains, and tweed, dominate the surface structure of BaTiO3 at room temperature. The surface ferroic signatures are maintained on heating to temperature (~550 K), well above the transition temperature (393 K). This surface proximity effect provides the mechanism for memory of the bulk ferroelectric domain arrangement up to 150 K above TC and thus can be considered as a robust fingerprint of the ferroelectric state near the surface. Self-reversal of polarization is observed for the tweed below TC and for the surface domains above TC. Annealing at higher temperature triggers the dynamic tweed which in turn allows a full reorganization of the ferroic domain configuration. [ABSTRACT FROM AUTHOR]

In this work, VO 2 (M1/R) thin films were exploited as H 2 gas sensors. A flat film morphology, obtained by furnace annealing, was compared with a laser-induced nanostructured one. The combination of the environmentally friendly sol-gel approach with the ultrafast laser crystallization allows for significant reductions in energy consumption and related emissions during the fabrication of VO 2 sensors. By decorating the sensors' surface with Pt nanoparticles (NPs), the sensor response was enhanced exploiting the hydrogen spillover effect. The Pt/VO 2 sensors, tested at operating temperatures between 20 and 200 °C and for concentration of H 2 from few ppm to 50000 ppm, offered a dual chemoresistive and optical sensing mode. Low operating temperatures of 150 °C were achieved, along with a detection limit as low as 2 ppm and a perfect baseline recovery. Both sensors guaranteed specific selectivity toward H 2 , without response to NO 2 or humidity, and long-term stability over 500 h. The H 2 sensing mechanism, for both the monoclinic and rutile VO 2 phases, was investigated through in operando X-ray Diffraction and in situ X-ray Photoelectron Spectroscopy tests. The interaction was found to be based on the reversible formation of H x VO 2 bronze, along with the reversible variations in the oxidation state of V.

The interaction of water with solid surfaces is crucial for a wide range of disciplines, including catalysis, environmental science, corrosion, geology, and biology. In this study, we present a combined experimental and theoretical investigation that elucidates the interaction of water with a model iron oxide surface under near ambient conditions (i.e., room temperature and water vapor in the mbar range). Our findings reveal that surface hydroxylation can be controlled at the nanoscale by the local properties of the oxide film, such as local rumpling and electrostatic potential. The iron oxide surface presents alternating hydrophilic and hydrophobic domains, creating after water exposure a hexagonal pattern with a pitch of approximately 3 nm, where the highly hydroxylated regions act as nucleation centers for nanoconfined water molecule clusters.

Many emerging commercial services are based on the sharing or pooling of resources for common use with the aim of reducing costs. Businesses such as delivery-, mobility-, or transport-as-a-service have become standard in many parts of the world, fulfilling on-demand requests for customers in live settings. However, it is known that many of these problems are NP-hard, and therefore both modeling and solving them accurately is a challenge. Here we focus on one such routing problem, the Ride Pooling Problem (RPP), where multiple customers can request on-demand pickups and drop-offs from shared vehicles within a fleet. The combinatorial optimization task is to optimally pool customer requests using the limited set of vehicles, akin to a small-scale flexible bus route. In this work, we propose a quadratic unconstrained binary optimization (QUBO) program and introduce efficient formulation methods for the RPP to be solved using metaheuristics, and specifically emerging quantum optimization algorithms., (© 2024. The Author(s).)

We apply a topological material design concept for selecting a bulk topology of 3D crystals by different van der Waals stackings of 2D topological insulator layers, and find a bismuth halide Bi_{4}Br_{2}I_{2} to be an ideal weak topological insulator (WTI) with the largest band gap (∼300  meV) among all the WTI candidates, by means of angle-resolved photoemission spectroscopy (ARPES), density functional theory (DFT) calculations, and resistivity measurements. Furthermore, we reveal that the topological surface state of a WTI is not "weak" but rather robust against external perturbations against the initial theoretical prediction by performing potassium deposition experiments. Our results vastly expand future opportunities for fundamental research and device applications with a robust WTI.

Stacking monolayer semiconductors creates moiré patterns, leading to correlated and topological electronic phenomena, but measurements of the electronic structure underpinning these phenomena are scarce. Here, we investigate the properties of the conduction band in moiré heterobilayers of WS 2 /WSe 2 using submicrometer angle-resolved photoemission spectroscopy with electrostatic gating. We find that at all twist angles the conduction band edge is the K -point valley of the WS 2 , with a band gap of 1.58 ± 0.03 eV. From the resolved conduction band dispersion, we deduce an effective mass of 0.15 ± 0.02 m e . Additionally, we observe replicas of the conduction band displaced by reciprocal lattice vectors of the moiré superlattice. We argue that the replicas result from the moiré potential modifying the conduction band states rather than final-state diffraction. Interestingly, the replicas display an intensity pattern with reduced 3-fold symmetry, which we show implicates the pseudo vector potential associated with in-plane strain in moiré band formation.

The quest for economically sustainable electrocatalysts to replace critical materials in anodes for the oxygen evolution reaction (OER) is a key goal in electrochemical conversion technologies, and, in this context, metal-organic frameworks (MOFs) offer great promise as alternative electroactive materials. In this study, a series of nanostructured electrocatalysts was successfully synthesized by growing tailored Ni-Fe-based MOFs on nitrogen-doped graphene, creating composite systems named MIL-NG-n. Their growth was tuned using a molecular modulator, revealing a non-trivial trend of the properties as a function of the modulator quantity. The most active material displayed an excellent OER performance characterized by a potential of 1.47 V (vs. RHE) to reach 10 mA cm -2 , a low Tafel slope (42 mV dec -1 ), and a stability exceeding 18 h in 0.1 M KOH. This outstanding performance was attributed to the synergistic effect between the unique MOF architecture and N-doped graphene, enhancing the amount of active sites and the electron transfer. Compared to a simple mixture of MOFs and N-doped graphene or the deposition of Fe and Ni atoms on the N-doped graphene, these hybrid materials demonstrated a clearly superior OER performance.

Understanding the interactions between amines and the surface of gold nanoparticles is important because of their role in the stabilization of the nanosystems, in the formation of the protein corona, and in the preparation of semisynthetic nanozymes. By using fluorescence spectroscopy, electrochemistry, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, and molecular simulation, a detailed picture of these interactions is obtained. Herein, it is shown that amines interact with surface Au(0) atoms of the nanoparticles with their lone electron pair with a strength linearly correlating with their basicity corrected for steric hindrance. The kinetics of binding depends on the position of the gold atoms (flat surfaces or edges) while the mode of binding involves a single Au(0) with nitrogen sitting on top of it. A small fraction of surface Au(I) atoms, still present, is reduced by the amines yielding a much stronger Au(0)-RN. + (RN . , after the loss of a proton) interaction. In this case, the mode of binding involves two Au(0) atoms with a bridging nitrogen placed between them. Stable Au nanoparticles, as those required for robust semisynthetic nanozymes preparation, are better obtained when the protein is involved (at least in part) in the reduction of the gold ions., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

The Large Plasma Device (LAPD) at UCLA (University of California, Los Angeles) produces an 18 m long, magnetized, quiescent, and uniform plasma at a high repetition rate to enable studies of fundamental plasma physics. Here, we report on a major upgrade to the LAPD plasma source that allows for more robust operation and significant expansion of achievable plasma parameters. The original plasma source made use of a heated barium oxide (BaO) coated nickel sheet as an electron emitter. This source had a number of drawbacks, including a limited range of plasma density (≲4.0 × 1012 cm-3), a limited discharge duration (∼10 ms), and susceptibility to poisoning following oxygen exposure. The new plasma source utilizes a 38 cm diameter lanthanum hexaboride (LaB6) cathode, which has a significantly higher emissivity, allowing for a much larger discharge power density, and is robust to exposure to air. Peak plasma density of up to 3.0 × 1013 cm-33 in helium gas has been achieved. The typical operating pressure is ∼10-5 Torr, while dynamic pressure can be achieved through the gas-puffing technique. Discharges as long as 70 ms have been produced, enabling a variety of long-time-scale studies of processes, such as turbulent particle transport. The new source has been in continuous operation for 14 months, having survived air leaks, power outages that led to rapid temperature changes on the cathode and heater, and planned machine openings. We describe the design, construction, and initial operation of this novel new large-area LaB6 plasma source., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

Objectives: Neck pain is extremely common and represents a substantial economic burden to our society. We aimed to investigate risk factors for nondisabling and disabling neck pain in a large cohort of Italian adolescents with a cross-sectional study., Design: Six thousand two hundred eighty-one students (14-19 yrs old) answered an online questionnaire, investigating the following: anthropometric data, lifestyle-related items, neck pain frequency and intensity, need for medical examination, and several risk factors. Students who had to give up social activities because of neck complaints constituted the disabling neck pain group., Results: Our findings revealed that sex, age, sports practice, hours of sleep, and family history were risk factors ( P < 0.001) for neck pain in our cohort. Moreover, disabling neck pain group experienced neck pain more frequently ( P < 0.001) and with higher levels of pain ( P < 0.001) compared with the nondisabling group. The number of hours of sleep was the only risk factor that showed a trend to differ comparing the disabling neck pain group with the nondisabling neck pain one ( P = 0.057)., Conclusions: Different risk factors for neck pain were detected in a very large cohort of adolescents. This study may pave the way for future prospective studies and for the development of preventive strategies for neck pain in adolescents., To Claim Cme Credits: Complete the self-assessment activity and evaluation online at http://www.physiatry.org/JournalCME., Cme Objectives: Upon completion of this article, the reader should be able to: (1) Identify different risk factors for neck pain in adolescents; (2) Determine the differences between adolescents with nondisabling neck pain and disabling neck pain; and (3) Recognize that most risk factors for disabling neck pain are still unknown, but insufficient sleep quantity could potentially contribute to the development of this condition., Level: Advanced., Accreditation: The Association of Academic Physiatrists is accredited by the Accreditation Council for Continuing Medical Education to provide continuing medical education for physicians.The Association of Academic Physiatrists designates this Journal-based CME activity for a maximum of 1.0 AMA PRA Category 1 Credit(s) ™. Physicians should only claim credit commensurate with the extent of their participation in the activity., Competing Interests: Financial disclosure statements have been obtained, and no conflicts of interest have been reported by the authors or by any individuals in control of the content of this article., (Copyright © 2022 Wolters Kluwer Health, Inc. All rights reserved.)

Heterostructures of Ga[Formula: see text]O[Formula: see text] with other materials such as Si, SiC or diamond, are a possible way of addressing the low thermal conductivity and lack of p-type doping of Ga[Formula: see text]O[Formula: see text] for device applications, as well as of improving device reliability. In this work we study the electrical and thermal properties of Ga[Formula: see text]O[Formula: see text]-SiO[Formula: see text] heterostructures. Here, thin-film gallium oxide with thickness ranging between 8 and 30 nm was deposited onto a silicon substrate with a thermal oxide by means of oxidised liquid gallium layer delamination. The resulting heterostructure is then characterised by means of X-ray photoelectron spectroscopy and transient thermoreflectance. The thin-film gallium oxide valence band offset with respect to the SiO[Formula: see text] is measured as 0.1 eV and predicted as [Formula: see text] eV with respect to diamond. The thin-film's out-of-plane thermal conductivity is determined to be 3 ±0.5 Wm[Formula: see text] K[Formula: see text], which is higher than what has been previously measured for other polycrystalline Ga[Formula: see text]O[Formula: see text] films of comparable thickness., (© 2023. The Author(s).)

In this work, mixed Ni/Co and Ni/Fe metal phosphides with different metal ratios were synthesized through the phosphidization of high-surface-area hydroxides grown hydrothermally on carbon cloth. The materials were characterized by means of X-ray photoemission spectroscopy, X-ray diffraction, energy dispersive X-ray analysis, and electron microscopies. The electrocatalytic performance in the electrochemical water splitting was tested in alkaline media. With the aim of determining the chemical stability of the mixed phosphides and the possible changes undergone under catalytic conditions, the materials were characterized before and after the electrochemical tests. The best performances in the hydrogen evolution reaction were achieved when synergic interactions are established among the metal centers, as suggested by the outstanding performances (50 mV to achieve 10 mA/cm 2 ) of materials containing the highest amount of ternary compounds, i.e., NiCoP and NiFeP. The best performances in the oxygen evolution reaction were reached by the Ni-Fe materials. Under these conditions, it was demonstrated that a strong oxidation of the surface and the dissolution of the phosphide/phosphate component takes place, with the consequent formation of the corresponding metal oxides and hydroxides.

As a semiconductor used for the photocatalytic hydrogen evolution reaction (HER), BiOBr has received intensive attention in recent years. However, the high recombination of photoexcited charge carriers results in poor photocatalytic efficiency. The combination with other photoactive semiconductors might represent a valuable approach to deal with the intrinsic limitations of the material. Given that BiOBr has a 2D structure, we propose a simple liquid-phase exfoliation method to peel BiOBr microspheres into few-layer nanosheets. By tuning the weight ratio between the precursors, we prepare a series of 2D MoS 2 /BiOBr van der Waals (vdW) heterojunctions and study their behaviour as (photo)electrocatalysts for the HER, finding dramatic differences as a function of weight composition. Moreover, we found that pristine 2D BiOBr and the heterojunctions, with the exception of the 1% MoS 2 /BiOBr composition, undergo photocorrosion, with BiOBr being reduced to metallic Bi. These findings provide useful guidelines to design novel 2D material-based (photo)electrocatalysts for the production of sustainable fuels.

Rhabdomyosarcoma (RMS) is an aggressive pediatric soft tissue sarcoma characterized by a very poor prognosis when relapses occur after front-line therapy. Therefore, a major challenge for patients' management remains the identification of markers associated with refractory and progressive disease. In this context, cancer autoantibodies are natural markers of disease onset and progression, useful to unveil novel therapeutic targets. Herein, we matched autoantibody profiling of alveolar RMS (ARMS) patients with genes under regulatory control of PAX3-FOXO1 transcription factor and revealed fibroblast growth factor 8 (FGF8) as a novel ARMS tumor antigen of diagnostic, prognostic, and therapeutic potential. We demonstrated that high levels of FGF8 autoantibodies distinguished ARMS patients from healthy subjects and represented an independent prognostic factor of better event-free survival. FGF8 was overexpressed in ARMS tumors compared to other types of pediatric soft tissue sarcomas, acting as a positive regulator of cell signaling. Indeed, FGF8 was capable of stimulating ARMS cells migration and expression of pro-angiogenic and metastasis-related factors, throughout MAPK signaling activation. Of note, FGF8 was found to increase in recurrent tumors, independently of PAX3-FOXO1 expression dynamics. Risk of recurrence correlated positively with FGF8 expression levels at diagnosis and reduced FGF8 autoantibodies titer, almost as if to suggest a failure of the immune response to control tumor growth in recurring patients. This study provides evidence about the crucial role of FGF8 in ARMS and the protective function of natural autoantibodies, giving new insights into ARMS biology and laying the foundations for the development of new therapeutic strategies., Competing Interests: The authors declare no conflict of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the decision to publish the results., (© 2022 The Author(s). Published with license by Taylor & Francis Group, LLC.)

A simple first-principles approach is used to estimate the core level shifts observed in X-ray photoelectron spectroscopy for the 4f electrons of Hf, Ta, W, and Re; these elements were selected because their 4f levels are relatively close to the Fermi energy. The approach is first tested by modeling the surface core level shifts of low-index surfaces of the four elemental metals, followed by its application to the well-studied material TaSe 2 in the commensurate charge density wave (CDW) phase, where agreement with experimental data is found to be good, showing that this approach can yield insights into modifications of the CDW. Finally, unterminated surface core level shifts in the hypothetical MXene Ta 3 C 2 are modeled, and the potential of XPS for the investigation of the surface termination of MXenes is demonstrated., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

The sub-bandgap levels associated with defect states in Cu 2 ZnSnS 4 (CZTS) thin films are investigated by correlating the temperature dependence of the absorber photoluminescence (PL) with the device admittance spectroscopy. CZTS thin films are prepared by thermolysis of molecular precursors incorporating chloride salts of the cations and thiourea. Na and Sb are introduced as dopants in the precursor layers to assess their impact on Cu/Zn and Sn site disorder, respectively. Systematic analysis of PL spectra as a function of excitation power and temperature show that radiative recombination is dominated by quasi-donor-acceptor pairs (QDAP) with a maximum between 1.03 and 1.18 eV. It is noteworthy that Sb doping leads to a transition from localized to delocalized QDAP. The activation energies obtained associated with QDAP emission closely correlate with the activation energies of the admittance responses in a temperature range between 150 K and room temperature in films with or without added dopants. Admittance data of CZTS films with no added dopants also have a strong contribution from a deeper state associated with Sn disorder. The ensemble of PL and admittance data, in addition to energy-filtered photoemission of electron microscopy (EF-PEEM), shows a detailed picture of the distribution of sub-bandgap states in CZTS and the impact of doping on their energetics and device performance., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Background: Many nonconclusive studies have been conducted on low back pain (LBP) in adolescents and associated factors., Objective: The aim was to assess the lifetime prevalence and associated factors of LBP in adolescents., Materials and Methods: A questionnaire was administered in high school students (14-19-yr-old participants) in Veneto region (Italy). The self-administered, structured questionnaire included anthropometric data; psychologic factors and lifestyle; presence, intensity, and family history of LBP; referral to professional health care for LBP; and a short version of the International Physical Activity Questionnaire., Results: A total of 6281 adolescents were recruited; 5204 questionnaires were included in the final analysis. A total of 2549 (48.98%) students reported one or more LBP episodes and 723 (13.89%) reported nonspecific disabling lumbar pain (i.e., no underlying pathology); 1040 (41.11%) subjects with LBP consulted a healthcare professional. A significant association emerged for LBP with sex (female), positive family history, time spent sitting or using electronic devices, sleep deprivation (<5 hrs/night), and low level of physical activity., Conclusion: In a large sample of adolescents, LBP lifetime prevalence is high and often associated with disabling pain and sedentary lifestyle, requiring professional care. These findings may support the development of prevention and treatment strategies of LBP in adolescents, reducing the risk of developing chronic pain., Competing Interests: Financial disclosure statements have been obtained, and no conflicts of interest have been reported by the authors or by any individuals in control of the content of this article., (Copyright © 2021 Wolters Kluwer Health, Inc. All rights reserved.)

The large-scale formation of patterned, quasi-freestanding graphene structures supported on a dielectric has so far been limited by the need to transfer the graphene onto a suitable substrate and contamination from the associated processing steps. We report μm scale, few-layer graphene structures formed at moderate temperatures (600-700 °C) and supported directly on an interfacial dielectric formed by oxidizing Si layers at the graphene/substrate interface. We show that the thickness of this underlying dielectric support can be tailored further by an additional Si intercalation of the graphene prior to oxidation. This produces quasi-freestanding, patterned graphene on dielectric SiO 2 with a tunable thickness on demand, thus facilitating a new pathway to integrated graphene microelectronics.

Alveolar rhabdomyosarcoma (ARMS) is a highly aggressive subtype of childhood cancer for which efficacious treatments are needed. Immunotherapy represents a new therapeutic opportunity to pursue, but it requires the identification of worthwhile tumor antigens. Herein, we exploited the capacity of ARMS autoantibodies to recognize tumor self-antigens, probing human protein microarrays with plasma from ARMS patients and healthy subjects. We assessed the autoantibody response in ARMS, validated data with independent techniques, and estimated autoantibodies diagnostic and prognostic significance by receiver-operator characteristic curves (ROC), uni- and multivariate analysis. Of the 48 tumor antigens identified, General Transcription Factor II-I (GTF2i) and Protocadherin Gamma Subfamily C5 (PCDHGC5) were selected as candidate targets to validate tumor-restricted antigen expression and autoantibody reactivity through an independent technique and wider cohort of cases. GTF2i and PCDHGC5 overexpression was observed in tumor tissues compared to normal counterparts, and anti-GTF2i and -PCDHGC5 autoantibodies were found able to distinguish ARMS patients from healthy subjects as well as cases with different histology. Moreover, low levels of PCDHGC5 autoantibodies characterized patients with worse event-free survival and proved to be an independent negative prognostic factor. This approach provided the first comprehensive autoantibody profile of ARMS, gave novel insights into the immune response of this malignancy and paved the way toward novel potential antibody-based therapeutic applications suitable to improve the survival of ARMS patients., (© 2021 The Author(s). Published with license by Taylor & Francis Group, LLC.)

Falls are the second most frequent cause of injury in the elderly. Physiological processes associated with aging affect the elderly's ability to respond to unexpected balance perturbations, leading to increased fall risk. Every year, approximately 30% of adults, 65 years and older, experiences at least one fall. Investigating the neurophysiological mechanisms underlying the control of static and dynamic balance in the elderly is an emerging research area. The study aimed to identify cortical and muscular correlates during static and dynamic balance tests in a cohort of young and old healthy adults. We recorded cortical and muscular activity in nine elderly and eight younger healthy participants during an upright stance task in static and dynamic (core board) conditions. To simulate real-life dual-task postural control conditions, the second set of experiments incorporated an oddball visual task. We observed higher electroencephalographic (EEG) delta rhythm over the anterior cortex in the elderly and more diffused fast rhythms (i.e., alpha, beta, gamma) in younger participants during the static balance tests. When adding a visual oddball, the elderly displayed an increase in theta activation over the sensorimotor and occipital cortices. During the dynamic balance tests, the elderly showed the recruitment of sensorimotor areas and increased muscle activity level, suggesting a preferential motor strategy for postural control. This strategy was even more prominent during the oddball task. Younger participants showed reduced cortical and muscular activity compared to the elderly, with the noteworthy difference of a preferential activation of occipital areas that increased during the oddball task. These results support the hypothesis that different strategies are used by the elderly compared to younger adults during postural tasks, particularly when postural and cognitive tasks are combined. The knowledge gained in this study could inform the development of age-specific rehabilitative and assistive interventions.

Severe acquired brain injury (ABI) is a major cause of long-term disability and is the main determinant of health and societal costs. Early identification of favourable long-term recovery would allow personalized rehabilitative programs and better health care resources allocation. In light of the higher survival rate from intensive care units (ICU) in recent years, there is a growing need for early prognostication markers of functional recovery; to date, these data have been mainly collected at rehabilitation unit admission and not during the acute phase. We present the protocol and methodology to develop prediction models in people with severe acquired brain injury (GCS at admission to ICU < 8) for the functional and cognitive outcome at 12 months from the event. Predictors will be collected during the acute stage. Participants will be recruited within the first 72 h from the event in the ICUs of two teaching hospitals (Padova and Treviso). Participants will be followed up at discharge from ICU, admission and discharge from Neurorehabilitation and after 12 months from the event. Clinical and functional scales, electroencephalography, evoked potentials, magnetic resonance imaging and serological markers will be entered into a digital registry. Survival will be estimated using the Cox proportional hazard model. A multivariate prediction model will be developed for each of the functional and cognitive outcomes at 12 months from the event.

Fibromyalgia syndrome (FMS) is a complex pain disorder, characterized by diffuse pain and cognitive disturbances. Abnormal cortical oscillatory activity may be a promising biomarker, encouraging non-invasive neurostimulation techniques as a treatment. We aimed to modulate abnormal slow cortical oscillations by delivering transcranial alternating current stimulation (tACS) and physiotherapy to reduce pain and cognitive symptoms. This was a double-blinded, randomized, crossover trial conducted between February and September 2018 at the Rehabilitation Unit of a teaching Hospital (NCT03221413). Participants were randomly assigned to tACS or random noise stimulation (RNS), 5 days/week for 2 weeks followed by ad hoc physiotherapy. Clinical and cognitive assessments were performed at T 0 (baseline), T 1 (after stimulation), T 2 (1 month after stimulation). Electroencephalogram (EEG) spectral topographies recorded from 15 participants confirmed slow-rhythm prevalence and provided tACS tailored stimulation parameters and electrode sites. Following tACS, EEG alpha1 ([8-10] Hz) activity increased at T 1 (p = 0.024) compared to RNS, pain symptoms assessed by Visual Analog Scale decreased at T 1 (T 1 vs T 0 p = 0.010), self-reported cognitive skills and neuropsychological scores improved both at T 1 and T 2 (Patient-Reported Outcomes in Cognitive Impairment, T 0 -T 2 , p = 0.024; Everyday memory questionnaire, T 1 compared to RNS, p = 0.012; Montréal Cognitive Assessment, T 0 vs T 1 , p = 0.048 and T 0 vs T 2 , p = 0.009; Trail Making Test B T 0 -T 2 , p = 0.034). Psychopathological scales and other neuropsychological scores (Trail Making Test-A; Total Phonemic Fluency; Hopkins Verbal Learning Test-Revised; Rey-Osterrieth Complex Figure) improved both after tACS and RNS but earlier improvements (T 1 ) were registered only after tACS. These results support tACS coupled with physiotherapy in treating FMS cognitive symptoms, pain and subclinical psychopathology.

Rhabdomyosarcoma (RMS) arises from myogenic precursors that fail to complete muscle differentiation and represents the most frequent soft tissue sarcoma in children. Two major histological subtypes are recognized: alveolar RMS, characterized by a more aggressive behavior and a greater proneness to metastasis, and embryonal RMS which accounts for the 80% of cases and carries a better prognosis. Despite the survival of patients with localized tumors has progressively improved, RMS remains a challenging disease especially for metastatic patients and in case of progressive or recurrent disease after front-line therapy. MicroRNAs, a class of small non-coding RNA, have emerged as crucial players in cancer development and progression, and their detection in plasma (circulating miRNAs) represents a promising minimally invasive approach that deserve to be exploited in clinical practice. We evaluated the utility of circulating miRNAs as diagnostic and prognostic biomarkers in children with RMS profiling miRNAs from plasma of a small cohort of RMS patients and healthy donors (HD) using a qPCR Cancer Panel. An assessment of hemolysis status of plasma using miR-451/miR-23a ratio was performed as pre-analytical analysis. Statistical analysis revealed that miRNAs expression pattern clearly distinguished RMS patients from HD ( p < 0.05). Interestingly, plasma levels of muscle-specific miR-206 were found to be significantly increased in RMS patients compared to HD, whereas levels of three potential tumor-suppressor miRNAs, miR-26a and miR-30b/30c, were found lower. Reduced levels of circulating miR-26a and miR-30b/c were further measured in an independent larger cohort of patients (validation set) by digital droplet PCR. In particular, we evidenced that miR-26a absolute plasma levels were associated with fusion status and adverse outcome ( p < 0.05). Taken together, these findings demonstrate the potential of circulating miRNA as diagnostic and prognostic biomarker in children affected by this malignancy and enforced the key role of miR-26a in pediatric rhabdomyosarcoma., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2020 Tombolan, Millino, Pacchioni, Cattelan, Zin, Bonvini and Bisogno.)

Background: Patient preferences regarding their involvement in shared treatments decisions is fundamental in clinical practice. Previous evidences demonstrated a large heterogeneity in these preferences. However, only few studies have analysed the influence of patients' individual differences, contextual and situational qualities, and their complex interaction in explaining this variability., Methods: We assessed the role of the interaction of patient's sociodemographic and psychological factors with a physician's gender. Specifically, we focused on patient gender and attitudes toward male or female physicians. One hundred fifty-three people participated in this randomised controlled study and were randomly assigned to one of two experimental conditions in which they were asked to imagine discussing their treatment with a male and a female doctor., Results: Analyses showed an interplay between attitude towards women and the gender of patients and doctors, explaining interindividual variability in patient preferences., Conclusions: In conclusion, patients' attitudes toward the physicians' gender constitutes a relevant characteristic that may influence the degree of control patients want to have and the overall patient-physician relationship., (© 2020 The Authors. Applied Psychology: Health and Well-Being published by John Wiley & Sons Ltd on behalf of International Association of Applied Psychology.)

Thermionic emission relies on the low work function and negative electron affinity of the, often functionalized, surface of the emitting material. However, there is little understanding of the interplay between thermionic emission and temperature-driven dynamic surface transformation processes as these are not represented on the traditional Richardson-Dushman equation for thermionic emission. Here, we show a new model for thermionic emission that can reproduce the effect of dynamic surface changes on the electron emission and correlate the components of the thermionic emission with specific surface reconstruction phases on the surface of the emitter. We use hydrogenated <100> single-crystal and polycrystalline diamonds as thermionic emitters to validate our model, which shows excellent agreement with the experimental data and could be applicable to other emitting materials. Furthermore, we find that tailoring the coverage of specific structures of the C(100)-(2 × 1):H surface reconstruction could increase the thermionic emission of diamond by several orders of magnitude.

Insulin-like growth factor-binding protein 2 (IGFBP2) is a tumor-associated protein measurable in patients' biopsies and blood samples. Increased IGFBP2 expression correlates with tumor severity in rhabdomyosarcoma (RMS). Thus, we examined the plasmatic IGFBP2 levels in 114 RMS patients and 15 healthy controls by ELISA assay in order to evaluate its value as a plasma biomarker for RMS. Additionally, we looked for the presence of a humoral response against IGBFP2 protein measurable by the production of anti-IGFBP2 autoantibodies. We demonstrated that both circulating IGFBP2 protein and autoantibodies were significantly higher in RMS patients with respect to controls and their combination showed a better discriminative capacity. IGFBP2 protein identified metastatic patients with worse event-free survival, whereas both IGFBP2 and anti-IGFBP2 antibodies negatively correlated with overall survival. Our study suggests that IGFBP2 and anti-IGFBP2 antibodies are useful for diagnostic and prognostic purposes, mainly as independent negative prognostic markers in metastatic patients. This is the first study that reports a specific humoral response in RMS plasma samples and proves the value of blood-based biomarkers in improving risk assessment and outcome of metastatic RMS patients., Competing Interests: The authors declare no conflict of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or in the decision to publish the results.

The development of programmable microscale materials with cell-like functions, dynamics and collective behaviour is an important milestone in systems chemistry, soft matter bioengineering and synthetic protobiology. Here, polymer/nucleotide coacervate micro-droplets are reconfigured into membrane-bounded polyoxometalate coacervate vesicles (PCVs) in the presence of a bio-inspired Ru-based polyoxometalate catalyst to produce synzyme protocells (Ru 4 PCVs) with catalase-like activity. We exploit the synthetic protocells for the implementation of multi-compartmentalized cell-like models capable of collective synzyme-mediated buoyancy, parallel catalytic processing in individual horseradish peroxidase-containing Ru 4 PCVs, and chemical signalling in distributed or encapsulated multi-catalytic protocell communities. Our results highlight a new type of catalytic micro-compartment with multi-functional activity and provide a step towards the development of protocell reaction networks.

Background: Pediatric oncohematologic patients are a high-risk population for clinical deterioration that might require pediatric intensive care unit (PICU) admission. Several studies have described outcomes and mortality predictors for patients post hematopoietic stem cell transplantation (HSCT), but fewer data exist regarding the category of non-HSCT patients., Procedure: All oncohematologic non-HSCT patients ≤18 years requiring PICU admission from 1998 to 2015 in our tertiary-care academic hospital were retrospectively evaluated by means of the pediatric hematology-oncology unit database and the Italian PICUs data network database. We assessed the relation between demographic and clinical characteristics and 90-day mortality after PICU admission., Results: Of 3750 hospitalized oncohematologic patients, 3238 were non-HSCT and 63 (2%) of them were admitted to the PICU. Patients were mainly affected by hematological malignancies (70%) and mostly were in the induction-therapy phase. The main reasons for admission were respiratory failure (40%), sepsis (25%), and seizures (16%). The median PICU stay was 5 days (range 1-107). The mortality rate at PICU discharge was 30%, and at 90 days it was 35%. Fifty-five percent of deaths happened in the first 2 days of the PICU stay. Cardiac arrest (P = .007), presence of disseminated intravascular coagulation (DIC, P = .007), and acute kidney injury (AKI) at PICU admission (P < .001) and during PICU stay (P = .021) were significant predictors of mortality in the multivariate analysis. Respiratory failure and mechanical ventilation were not associated with mortality., Conclusions: A relatively small percentage of non-HSCT patients required PICU admission, but the mortality rate was still high. Hemodynamic instability, DIC, and AKI, but not respiratory failure, were significant predictors of mortality., (© 2019 Wiley Periodicals, Inc.)

The photoemission electron microscopy and x-ray photoemission spectroscopy were utilized for the study of anodized epitaxial graphene (EG) on silicon carbide as a fundamental aspect of the oxygen evolution reaction on graphitic materials. The high-resolution analysis of surface morphology and composition quantified the material transformation during the anodization. We investigated the surface with lateral resolution <150 nm, revealing significant transformations on the EG and the role of multilayer edges in increasing the film capacitance.

We compare electrochemically modified or thiol-functionalized single-crystal samples of the topological insulator (TI) Bi 2 Te 0.9 Se 2.1 to freshly cleaved/air-exposed control samples and use X-ray photoelectron spectroscopy (XPS) to investigate the extent of any surface oxidation. XPS spectra for a TI sample maintained at an appropriate potential for 2 h demonstrate the feasibility of protecting the TI surface from oxidation while working in an electrochemical environment. Deliberate electrochemical oxidation, in contrast, generates prominent Bi, Te, and Se peaks associated with oxidation. However, this change is reversible, as further XPS spectra following electrochemical reduction are similar to those measured for an in situ cleaved sample. XPS also shows that adsorption of pentanedithiol (PDT) protects the TI surface from oxidation. Cyclic voltammetry shows that PDT adsorption suppresses electrochemical oxidation and reduction, while electrochemical impedance spectroscopy shows that it increases the charge transfer resistance significantly. Our work demonstrates the ability to control and characterize the surface chemistry of single-crystal TIs in an electrochemical environment for the first time.

Abnormal cortical oscillations are markers of Parkinson's Disease (PD). Transcranial alternating current stimulation (tACS) can modulate brain oscillations and possibly impact on behaviour. Mapping of cortical activity (prevalent oscillatory frequency and topographic scalp distribution) may provide a personalized neurotherapeutic target and guide non-invasive brain stimulation. This is a cross-over, double blinded, randomized trial. Electroencephalogram (EEG) from participants with PD referred to Specialist Clinic, University Hospital, were recorded. TACS frequency and electrode position were individually defined based on statistical comparison of EEG power spectra maps with normative data from our laboratory. Stimulation frequency was set according to the EEG band displaying higher power spectra (with beta excess on EEG map, tACS was set at 4 Hz; with theta excess, tACS was set at 30 Hz). Participants were randomized to tACS or random noise stimulation (RNS), 5 days/week for 2-weeks followed by ad hoc physical therapy. EEG, motor (Unified Parkinson's Disease Rating Scale-motor: UPDRS III), neuropsychological (frontal, executive and memory tests) performance and mood were measured before (T 0 ), after (T 1 ) and 4-weeks after treatment (T 2 ). A linear model with random effects and Wilcoxon test were used to detect differences. Main results include a reduction of beta rhythm in theta-tACS vs. RNS group at T 1 over right sensorimotor area (p = .014) and left parietal area (p = .010) and at T 2 over right sensorimotor area (p = .004) and left frontal area (p = .039). Bradykinesia items improved at T 1 (p = .002) and T 2 (p = .047) compared to T 0 in the tACS group. In the tACS group the Montréal Cognitive Assessment (MoCA) improved at T 2 compared with T 1 (p = .049). Individualized tACS in PD improves motor and cognitive performance. These changes are associated with a reduction of excessive fast EEG oscillations., (Copyright © 2019 The Authors. Published by Elsevier Inc. All rights reserved.)

The performance of Cu 2 ZnSn(S,Se) 4 thin-film solar cells, commonly referred to as kesterite or CZTSSe, is limited by open-circuit voltage (V OC ) values less than 60% of the maximum theoretical limit. In the present study, we employ energy-filtered photoemission microscopy to visualize nanoscale shunting paths in solution-processed CZTSSe films, which limit the V OC of cells to approximately 400 mV. These studies unveil areas of local effective work function (LEWF) narrowly distributed around 4.9 eV, whereas other portions show hotspots with LEWF as low as 4.2 eV. Localized valence band spectra and density functional theory calculations allow rationalizing the LEWF maps in terms of the CZTSSe effective work function broadened by potential energy fluctuations and nanoscale Sn(S,Se) phases., (Copyright © 2018 The Author(s). Published by Elsevier Inc. All rights reserved.)

Graphene and h-BN are grown by chemical vapor deposition in ultra high vacuum conditions on the Pt(110) surface. Scanning tunneling microscopy measurements and low-energy electron diffraction data indicate that graphene forms a variety of differently oriented incommensurate domains although with a strong preference to align its [Formula: see text] direction with the [Formula: see text] direction of Pt. Meanwhile, h-BN exhibits a c(8 × 10) commensurate superstructure, which presents a high level of defectivity that implies local variation of the periodicity (i.e. mixed c(8 × 10) and c(8 × 12) patches) and the introduction of local defects. The combination of advanced photoemission spectroscopy data (angle-resolved photoemission spectroscopy from the valence band) and ab initio calculations indicates that both 2D materials interact weakly with the substrate: graphene exhibits neutral doping and is morphologically flat, even if it nucleates on the relatively highly corrugated rectangular (110) surface. In the case of h-BN, the interaction is slightly stronger and is characterized by a small electron transfer from surface Pt atoms to nitrogen atoms. The (110) termination of Pt is therefore a quite interesting surface for the growth of 2D materials because given its low symmetry, it may favor the growth of selectively oriented domains but does not affect their pristine electronic properties.

Chemically modified graphene⁻based materials (CMG) are currently attracting a vast interest in their application in different fields. In particular, heteroatom-doped graphenes have revealed great potentialities in the field of electrocatalysis as substitutes of fuel cell noble metal⁻based catalysts. In this work, we investigate an innovative process for doping graphene nanostructures. We optimize a novel synthetic route based on aerosol preparation, which allows the simultaneous doping, crumpling, and reduction of graphene oxide (GO). Starting from aqueous solutions containing GO and the dopant precursors, we synthesize N- and N,S-dual-doped 3D graphene nanostructures (N-cGO and N,S-cGO). In the aerosol process, every aerosol droplet can be considered as a microreactor where dopant precursors undergo thermal decomposition and react with the GO flakes. Simultaneously, thanks to the relatively high temperature, GO undergoes crumpling and partial reduction. Using a combination of spectroscopic and microscopic characterization techniques, we investigate the morphology of the obtained materials and the chemical nature of the dopants within the crumpled graphene sheets. This study highlights the versatility of the aerosol process for the design of new CMG materials with tailored electrocatalytic properties.

In this paper, a perspective on the application of Spatially- and Angle-Resolved PhotoEmission Spectroscopy (ARPES) for the study of two-dimensional (2D) materials is presented. ARPES allows the direct measurement of the electronic band structure of materials generating extremely useful insights into their electronic properties. The possibility to apply this technique to 2D materials is of paramount importance because these ultrathin layers are considered fundamental for future electronic, photonic and spintronic devices. In this review an overview of the technical aspects of spatially localized ARPES is given along with a description of the most advanced setups for laboratory and synchrotron-based equipment. This technique is sensitive to the lateral dimensions of the sample. Therefore, a discussion on the preparation methods of 2D material is presented. Some of the most interesting results obtained by ARPES are reported in three sections including: graphene, transition metal dichalcogenides (TMDCs) and 2D heterostructures. Graphene has played a key role in ARPES studies because it inspired the use of this technique with other 2D materials. TMDCs are presented for their peculiar transport, optical and spin properties. Finally, the section featuring heterostructures highlights a future direction for research into 2D material structures.