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Next-generation batteries based on sustainable multivalent working ions, such as Mg2+, Ca2+, or Zn2+, have the potential to improve the performance, safety, and capacity of current battery systems. Development of such multivalent ion batteries is hindered by a lack of understanding of multivalent ionics in solids, which is crucial for many aspects of battery operation. For instance, multivalent ionic transport was assumed to be correlated with electronic transport; however, we have previously shown that Zn2+can conduct in electronically insulating ZnPS3with a low activation energy of 350 meV, albeit with low ionic conductivity. Here, we show that exposure of ZnPS3to environments with water vapor at different relative humidities results in room-temperature conductivity increases of several orders of magnitude, reaching as high as 1.44 mS cm–1without decomposition or structural changes. We utilize impedance spectroscopy with ion selective electrodes, ionic transference number measurements, and deposition and stripping of Zn metal, to confirm that both Zn2+and H+act as mobile ions. The contribution from Zn2+to the ionic conductivity in water vapor exposed ZnPS3is high, representing superionic Zn2+conduction. The present study demonstrates that it is possible to enhance multivalent ion conduction of electronically insulating solids as a result of water adsorption and highlights the importance of ensuring that increased conductivity in water vapor exposed multivalent ion systems is in fact due to mobile multivalent ions and not solely H+.

Selection of corrosion-resistant, cost-effective structural materials for the process and containment vessels required for the production, upgrading, and storage of biomass-derived oils has been the subject of study in our laboratory for many years. The wide variety of biomass resources and the many liquefaction techniques and processing conditions result in products with a broad range of properties and compositions. This paper will address the materials issues in three distinct areas. In production, materials are exposed to temperatures that range from 350 to 550 °C depending upon the process. Generally, austenitic stainless steels have performed reasonably well, although thicker oxide scales and intergranular attack have sometimes been observed. For storage and transport of the bio-oil products, temperatures experienced by the containment materials are not expected to exceed 50 °C. Our studies have shown that most raw bio-oils contain significant concentrations of organic acids, and low-molecular-weight organic acids were quite corrosive to carbon and low alloy steels. For some applications, subsequent processing is required, which includes hydrotreating or co-processing with a petroleum-derived liquid. These processes utilize a catalyst that requires periodic retreatment with a sulfidizing gas, and the exposure to this gas at elevated temperatures can cause appreciable corrosion to the more common austenitic stainless steels. The materials considered most cost-effective and sufficiently corrosion-resistant for each of these environments were identified.

High levels of HIV testing in men who have sex with men remain key to reducing the incidence of HIV. We aimed to assess whether the offer of a single, free HIV self-testing kit led to increased HIV diagnoses with linkage to care.

Over the course of more than three decades, Li-ion batteries have come to revolutionize the way we store and transport energy. These incredibly compact electrochemical devices rely fundamentally on the ability to reversibly insert lithium ions into densely packed arrangements of atoms. Of the tens of thousands of materials reported in the structural databases, only a very small number have been shown to be capable of accommodating the kind of fast ionic diffusion necessary to operate in practical devices. In honor of John B. Goodenough’s 100th birthday, this perspective will overview the current understanding of the kinds of structural features that help and/or hurt fast lithium ion transport through insertion hosts, with a particular focus on the role that the rotation of rigid subunits plays in the movement of lithium through the solid state.

AbstractThis study examined the use of an iPhone and the List Recorder Application to teach three adolescents with autism spectrum disorder to acquire, maintain, and generalize interpersonal daily living skills (DLS) in a community setting. A multiple probe design across participants was used to teach participants to use interpersonal DLS to order and purchase coffee and a snack. All three participants demonstrated an increase in their use of interpersonal skills in the community. Participants were able to maintain these skills once the intervention was removed during follow-up and to generalize these skills to a novel community setting. Results indicate that the use of mobile technology can effectively be used to teach DLS, inclusive of interpersonal skills, entirely in a community setting.

The vast majority of peatlands in Southeast Asia are located in Indonesia. They are currently classified as degraded and at risk of fire. Fire prevention and the restoration of degraded peatlands have therefore been part of the national government's agenda for the last two presidential terms. With the immense pressure of anthropogenic challenges, interventions to restore degraded peatlands and prevent fire combine biophysical and socioeconomic considerations. This paper explores the implementation of community-focused interventions and participatory processes in fire prevention, peatland restoration and sustainable livelihood improvement in Bengkalis Regency, Riau Province. We used Participatory Action Research (PAR) and an Institutional Analysis and Development (IAD) framework to foster an on-the-ground and inclusive process for behavioral changes that result in not using fire in agricultural land preparation and to advance awareness of and participation in restoring degraded peatlands. Our findings reveal that PAR, with an IAD framing, can catalyze change. Four critical aspects are required for this: (a) demand for the intervention; (b) adequate political support; (c) community participation, leadership, social capital and local institutions; and (d) business models for sustainable livelihood transitions. This paper provides lessons on scientifically driven and evidence-based participatory processes for restoration.

This work investigated the corrosivity of biomass-derived liquid fuels and organic acids associated with bio-oils and conducted a corrosion compatibility evaluation of several structural ferrous alloys in the fuels and acids. The acidity parameters and solution conductivity values were higher in raw pyrolysis bio-oils than postprocessed oils with significant corrosion attack for carbon steel and Fe-2.25Cr-1Mo. However, higher-grade stainless steels, ferritic Fe-15Cr (15Cb) and austenitic types 304L and 316L, showed negligible corrosion loss, whereas lower-Cr ferritic grades 409, 410, and 416 were attacked. Metal leaching tests and electrochemical impedance spectroscopy measurements revealed superior corrosion resistance of 316 over 410 stainless steels in solutions of formic and oxalic acids that can be present in bio-oils. The corrosion evaluation methods utilized in this work provide effective screening tools to identify the compatible structural alloys for bio-oils.

To better understand and evaluate the corrosion performance of candidate structural steels and ferritic stainless steels for production, transport, and storage of biomass pyrolysis oils, corrosion studies were conducted in selected organic constituents of bio-oils, including catechol, formic acid, and their mixtures as well as lactobionic acid, using electrochemical impedance spectroscopy. R2, the resistance against corrosion reaction, was obtained by fitting measured impedance spectra into an equivalent circuit. The values of R2were then used to assess corrosion resistance of the steels in each organic constituent and mixture. Type 410 and 430 stainless steels were resistant to corrosion in all tested organic constituents, while 2.25Cr-1Mo steel was not. 9Cr-1Mo steel was corrosion resistant in catechol but not in the other mixtures that contained organic acids. On the basis of the results of this work, it is suggested that the corrosion resistance against organic acids is attributed to formation of a Cr-rich passive film that requires stainless steels with critical Cr levels in excess of approximately 11 wt %. In catechol-only solution, lower levels of Cr intermediate between that of 2.25Cr-1Mo steel and 9Cr-1Mo steel appeared sufficient.

Coaching in the school setting typically follows the traditional format of preconference, observe, and postconference, where feedback on teaching performance is shared but often delayed. Professional development (PD) provides teachers with skills to enhance their teaching practice with little to no follow-up or support. The most effective way to produce change in the school setting is to show the connection between PD and student performance, and iCoaching can help to bridge the gap. In this study, four teachers participated in a focused PD session and subsequent iCoaching sessions where the researcher used iPods and Bluetooth earbuds as a bug-in-ear (BIE) device. A coach served as a live, remote observer providing coaching prompts to increase teacher-delivered opportunities to respond (OTR). The results indicated that iCoaching was effective in increasing teacher-delivered OTR and in increasing student responses and academic performance.

Background: We and others have reported a significant association between low vitamin D levels at diagnosis of indolent B-cell lymphomas and inferior overall survival; the magnitude of this association is stronger than conventional clinical prognostic features. Vitamin D insufficiency impairs rituximab-mediated cytotoxicity and impairs macrophage function, which impacts rituximab responses in vivo. We therefore conducted a phase III, double-bind study of oral cholecalciferol vs. placebo for three years in patients with indolent lymphoma treated with rituximab monotherapy.

The level of evidence for HIV transmission risk through condomless sex in serodifferent gay couples with the HIV-positive partner taking virally suppressive antiretroviral therapy (ART) is limited compared with the evidence available for transmission risk in heterosexual couples. The aim of the second phase of the PARTNER study (PARTNER2) was to provide precise estimates of transmission risk in gay serodifferent partnerships.

ABSTRACTNearly everyone agrees that physical pain is bad. Indeed, if anything merits the status of a platitude in our everyday thinking about value, the idea that pain is bad surely does. Equally, it seems clearly true that emotional suffering – despair, loneliness, grief, disappointment, guilt, shame, lovesickness, and the like – are all bad as well. We are strongly inclined to pity and feel sorry for those who suffer emotionally in these ways; we are motivated, at least some of the time, to do what we can to alleviate their suffering. Given this, it might seem curious that pain and suffering are so integral to sport – whether one is a participant or a spectator. There’s nothing particularly puzzling about pain and suffering that is inadvertentlyrelated to sport – as when an athlete injures her hamstring and has to miss her chance at Olympic glory, or when supporters face the misery of getting up at 6am because an away game has been scheduled to start at noon. But there does seem to be something curious about the extent to which pain and suffering are voluntarily embraced by participants and spectators, as the quotation from Nick Hornby aptly illustrates. Why do people willingly engage in something that brings about so much suffering? In this paper, I’ll attempt to answer this question.1

Plasma electrolytic oxidation (PEO) electro-ceramic (EC) coatings with and without an epoxy-base electro-coat (E-coat) overlayer were studied on four magnesium alloys using the same process deposition parameters: Mg-3Al-1Zn (AZ31B), Mg-9Al-0.5Zn (AZ91D), Mg-1.5Zn-0.3Zr-<0.5Nd (ZE10A, ZEK100 type), and Mg-4Y-(<2.5 Nd)-0.4Zr (WE43). A similar magnesium-fluoride (Mg-F) base EC chemistry formed on all four alloys. However, the morphology of the EC was significantly impacted by the substrate alloys, with higher alloy Al or Zr/rare earth (RE) levels also resulting in thicker coatings. A duplex EC structure formed on AZ31B, AZ91D, and ZE10, with a submicron inner layer and a thicker outer porous layer; whereas a striated multi-layer inner region and thick porous outer region formed on WE43. The EC coated alloys exhibited similar corrosion resistance to the bare alloys due to coating porosity, with the best corrosion resistance exhibited by AZ91D and WE43. After applying the E-coat overlayer, similar, excellent corrosion resistance was exhibited for all four EC + E-coated alloys. Scribing of the EC + E-coat to controllably introduce a coating defect degraded corrosion resistance, particularly for WE43, which suffered from E-coat blistering due to susceptibility of the inner striated EC layer to delamination.

The western U.S. is expected to experience more frequent and severe droughts as a result of climate change, with potentially large impacts on agricultural production and the economy. Irrigated farmers have multiple options for minimizing the impact of drought including switching to more efficient irrigation technologies. More efficient technologies that increase the fraction of the water available to the crop root zone would allow farmers to maintain current production levels with less water. However, these systems are capital intensive. The objective of this study is to explore when (and under what climatic conditions) it makes economic sense for farmers to invest in new irrigation systems. We examine this in the Yakima River Basin in Washington State of the U.S. We use VIC‐CropSyst, a large‐scale grid‐based modeling framework that mechanistically simulates hydrologic and agricultural processes. Water supply simulated by VIC‐CropSyst drives a river system and water management model (YAK‐RW). A computational platform was developed to perform the economic analysis for each grid cell, crop type, and future climate scenario separately, which allowed us to explore whether the implementation of more efficient irrigation systems would be economically viable. Our results indicate that investing in a more efficient irrigation system improves agricultural economy of the Yakima River Basin (9% −25%). We also show that at the farm level, more significant droughts can provide economic incentives for investment up to a point. For severe climate change projections, droughts become frequent and severe enough that economic benefits of improving water use efficiency do not exceed investment costs. Climate change increases the frequency and severity of drought; however, in some cases, this does not provide enough economic incentive for investment in a new irrigation systemAt the farm level, the viability of investment depends on crop type and severity of droughtsNet economic benefit at the basin scale depends on the cropping mix

Silver metal exposed to the atmosphere corrodes and becomes tarnished as a result of oxidation and precipitation of the metal as an insoluble salt. Tarnish has so poor a reputation that the word itself connotes corruption and disrespectability; however, tarnishing is a facile synthetic approach for preparing thin metal-sulfide films on silver or copper metal that might be exploited to prepare more elaborate materials with desirable optoelectronic properties. In this work, we prepare luminescent semiconducting thin films of mithrene, a metal–organic chalcogenolate assembly, by replacing the tarnish-causing atmospheric sulfur source with diphenyl diselenide. Mithrene, or silver benzeneselenolate [AgSePh]∞, is a crystalline solid that contains both an organic supramolecular phase and a two-dimensional inorganic coordination polymer phase. This compound gradually accumulates as the sole product of silver metal corrosion. The chemical reaction is carried out on metallic silver thin films and yields crystalline films with thicknesses ranging from 5 to 100 nm. We use the large-area films (>6 cm2) afforded by this method to measure the optical properties of this compound. The mild-temperature, wafer-scale processing of hybrid chalcogenolate thin films may prove useful in the application of hybrid organic–inorganic materials in semiconductor devices and hierarchical architectures.

Hydrogen gas is formed when Mg corrodes in water; however, the manner and extent to which the hydrogen may also enter the Mg metal is poorly understood. Such knowledge is critical as stress corrosion cracking (SCC)/embrittlement phenomena limit many otherwise promising structural and functional uses of Mg. Here, we report via D2O/D isotopic tracer and H2O exposures with characterization by secondary ion mass spectrometry, inelastic neutron scattering vibrational spectrometry, electron microscopy, and atom probe tomography techniques direct evidence that hydrogen rapidly penetrated tens of micrometers into Mg metal after only 4 h of exposure to water at room temperature. Further, technologically important microalloying additions of <1 wt % Zr and Nd used to improve the manufacturability and mechanical properties of Mg significantly increased the extent of hydrogen ingress, whereas Al additions in the 2–3 wt % range did not. Segregation of hydrogen species was observed at regions of high Mg/Zr/Nd nanoprecipitate density and at Mg(Zr) metastable solid solution microstructural features. We also report evidence that this ingressed hydrogen was unexpectedly present in the alloy as nanoconfined, molecular H2. These new insights provide a basis for strategies to design Mg alloys to resist SCC in aqueous environments as well as potentially impact functional uses such as hydrogen storage where increased hydrogen uptake is desired.

Various electroplated coatings from [Ni/Co]-Cr-[Mo/Fe] systems, were tested to assess their potential to enhance lifetime performance of low-cost stainless steels exposed to bio-combustor operating conditions. A wide range of electrodeposition processing conditions and electrolytes were evaluated based upon an ability to: (1) design REACH compliant electrolytes that enable a wide range of potentially corrosion resistant alloys to be electrodeposited; (2) scale the process to enable compositionally and structurally uniform coatings to be formed onto SS test pieces; and (3) maintain coating adherence and corrosion resistance during accelerated high temperature corrosion studies. Within this program we developed uniform, dense, well-adhered alloy coatings of various compositions, and performed accelerated high temperature corrosion studies to ascertain which alloys maintained better substrate adherence and corrosion resistance when exposed to salted thermal exposure conditions of 700oC for 500 h.

The aim of this study is to assess the performance of a computer-aided semi-automated algorithm we have adapted for the purpose of segmenting malignant pleural mesothelioma (MPM) on CT. Forty-five CT scans were collected from 15 patients (M:F $$=$$ = 10:5, mean age 62.8 years) in a multi-centre clinical drug trial. A computer-aided random walk-based algorithm was applied to segment the tumour; the results were then compared to radiologist-drawn contours and correlated with measurements made using the MPM-adapted Response Evaluation Criteria in Solid Tumour (modified RECIST). A mean accuracy (Sørensen–Dice index) of 0.825 (95% CI [0.758, 0.892]) was achieved. Compared to a median measurement time of 68.1 min (range [40.2, 102.4]) for manual delineation, the median running time of our algorithm was 23.1 min (range [10.9, 37.0]). A linear correlation (Pearson’s correlation coefficient: 0.6392, $$p < 0.05$$ p<0.05 ) was established between the changes in modified RECIST and computed tumour volume. Volumetric tumour segmentation offers a potential solution to the challenges in quantifying MPM. Computer-assisted methods such as the one presented in this study facilitate this in an accurate and time-efficient manner and provide additional morphological information about the tumour’s evolution over time.

Imaging biomarkers (IBs) are used extensively in drug development and cancer research, but important differences exist between IBs and biospecimen-derived biomarkers. A tailored 'roadmap' is required for the development of new IBs to be used either in clinical research or for decision-making in healthcare. In this Consensus statement, a group of experts assembled by CRUK and the EORTC present 14 key recommendations for accelerating the clinical translation of IBs.

ObjectiveTo develop a clinically useful model that estimates the 10 year risk of breast cancer related mortality in women (self-reported female sex) with breast cancer of any stage, comparing results from regression and machine learning approaches.DesignPopulation based cohort study.SettingQResearch primary care database in England, with individual level linkage to the national cancer registry, Hospital Episodes Statistics, and national mortality registers.Participants141 765 women aged 20 years and older with a diagnosis of invasive breast cancer between 1 January 2000 and 31 December 2020.Main outcome measuresFour model building strategies comprising two regression (Cox proportional hazards and competing risks regression) and two machine learning (XGBoost and an artificial neural network) approaches. Internal-external cross validation was used for model evaluation. Random effects meta-analysis that pooled estimates of discrimination and calibration metrics, calibration plots, and decision curve analysis were used to assess model performance, transportability, and clinical utility.ResultsDuring a median 4.16 years (interquartile range 1.76-8.26) of follow-up, 21 688 breast cancer related deaths and 11 454 deaths from other causes occurred. Restricting to 10 years maximum follow-up from breast cancer diagnosis, 20 367 breast cancer related deaths occurred during a total of 688 564.81 person years. The crude breast cancer mortality rate was 295.79 per 10 000 person years (95% confidence interval 291.75 to 299.88). Predictors varied for each regression model, but both Cox and competing risks models included age at diagnosis, body mass index, smoking status, route to diagnosis, hormone receptor status, cancer stage, and grade of breast cancer. The Cox model’s random effects meta-analysis pooled estimate for Harrell’s C index was the highest of any model at 0.858 (95% confidence interval 0.853 to 0.864, and 95% prediction interval 0.843 to 0.873). It appeared acceptably calibrated on calibration plots. The competing risks regression model had good discrimination: pooled Harrell’s C index 0.849 (0.839 to 0.859, and 0.821 to 0.876, and evidence of systematic miscalibration on summary metrics was lacking. The machine learning models had acceptable discrimination overall (Harrell’s C index: XGBoost 0.821 (0.813 to 0.828, and 0.805 to 0.837); neural network 0.847 (0.835 to 0.858, and 0.816 to 0.878)), but had more complex patterns of miscalibration and more variable regional and stage specific performance. Decision curve analysis suggested that the Cox and competing risks regression models tested may have higher clinical utility than the two machine learning approaches.ConclusionIn women with breast cancer of any stage, using the predictors available in this dataset, regression based methods had better and more consistent performance compared with machine learning approaches and may be worthy of further evaluation for potential clinical use, such as for stratified follow-up.

Magnesium(II) plays catalytic, structural, regulatory, and signaling roles in living organisms. Abnormal levels of this metal have been associated with numerous pathologies, including cardiovascular disease, diabetes, metabolic syndrome, immunodeficiency, cancer, and, most recently, liver pathologies affecting humans. The role of Mg2+in the pathophysiology of liver disease, however, has been occluded by concomitant changes in concentration of interfering divalent cations, such as Ca2+, which complicates the interpretation of experiments conducted with existing molecular Mg2+indicators. Herein, we introduce a new quinoline-based fluorescent sensor, MagZet1, that displays a shift in its excitation and emission wavelengths, affording ratiometric detection of cellular Mg2+by both fluorescence microscopy and flow cytometry. The new sensor binds the target metal with a submillimolar dissociation constant─well suited for detection of changes in free Mg2+in cells─and displays a 10-fold selectivity against Ca2+. Furthermore, the fluorescence ratio is insensitive to changes in pH in the physiological range, providing an overall superior performance over existing indicators. We provide insights into the metal selectivity profile of the new sensor based on computational modeling, and we apply it to shed light on a decrease in cytosolic free Mg2+and altered expression of metal transporters in cellular models of drug-induced liver injury caused by acetaminophen overdose.

Adults with mild autism spectrum disorder (ASD) face challenges in romantic relationships. Healthy romantic relationships yield physical and mental health benefits important to improved quality of life, yet many adults with ASD do not experience successful romantic relationships precluding them from possible benefits. This is the first study that explores the effects of group counseling, using the protocol Relationship Enhancement®, for 38 adult ASD participants in treatment as usual and a modified condition. Social skills, empathy, and social support were measured pre- and posttreatment. Results indicate improvements in social skills and empathy in both treatment conditions.