Synthesis of BaZrS3 and BaHfS3 Chalcogenide Perovskite Films Using Single-Phase Molecular Precursors at Moderate Temperatures.

Chalcogenide perovskites have garnered interest for applications in semiconductor devices due to their excellent predicted optoelectronic properties and stability. However, high synthesis temperatures have historically made these materials incompatible with the creation of photovoltaic devices. Here, we demonstrate the solution processed synthesis of luminescent BaZrS3 and BaHfS3 chalcogenide perovskite films using single-phase molecular precursors at sulfurization temperatures of 575 °C and sulfurization times as short as one hour. These molecular precursor inks were synthesized using known carbon disulfide insertion chemistry to create Group 4 metal dithiocarbamates, and this chemistry was extended to create species, such as barium dithiocarboxylates, that have never been reported before. These findings, with added future research, have the potential to yield fully solution processed thin films of chalcogenide perovskites for various optoelectronic applications.

Near-the-Line Steel Slag Analysis Using Laser-Induced Breakdown Spectroscopy: Traditional Univariate Versus Machine Learning Calibration Methods.

This work is focused on rapid quantitative analysis of slag in the steel industry for improved process control. The novel approach in this work is a direct comparison of two methods to calibrate and quantify spectral data from the slags. Calibration was first done with the most prevalent method in quantitative optical emission spectroscopy (OES) of solids, the univariate ratio method. The second method is an advanced multivariate analysis (MVA) algorithm termed Elastic Net, allowing to include several lines for each element in the calibration functions. In both methods, the output is mass fraction ratios of the analyte element (or compound) to a matrix element (compound). The actual mass fractions of each compound are calculated by sum normalization assuming the matrix to make up the difference up to 100%. The metric used to evaluate the performance of the methods in terms of accuracy is the parameter σrel calculated as the ratio of the root mean square (RMS) deviation from values obtained by X-ray fluorescence (XRF) divided by the average mass fraction of the compound, expressed in percent. A bit surprising, the main outcome of the comparison is that there is very little difference in the performance of the two methods. One exception is the analysis of MgO, where the elastic net gives significantly better accuracy. Presumably, this is due to the use of multiple lines for Mg to build the calibration function. This is very encouraging, since MgO is a major compound in most slags that needs to be determined accurately. It is suggested to improve accuracy further by means of separate calibrations for a limited number of slag types.

A global reconnaissance of particulates and metals/metalloids in untreated drinking water sources.

Metal and metalloid contamination in drinking water sources is a global concern, particularly in developing countries. This study used hollow membrane water filters and metal-capturing polyurethane foams to sample 71 drinking water sources in 22 different countries. Field sampling was performed with sampling kits prepared in the lab at Hope College in Holland, MI, USA. Filters and foams were sent back to the lab after sampling, and subsequent analysis of flushates and rinsates allowed the estimation of suspended solids and metal and other analayte concentrations in source waters. Estimated particulate concentrations were 0-92 mg/L, and consisted of quartz, feldspar, and clay, with some samples containing metal oxides or sulfide phases. As and Cu were the only analytes which occurred above the World Health Organization (WHO) guidelines of 10 µg/L and 2000 µg/L, respectively, with As exceeding the guideline in 45% of the sources and Cu in 3%. Except for one value of ~ 285 µg/L, As concentrations were 45-200 µg/L (river), 65-179 µg/L (well), and 112-178 µg/L (tap). Other metals (Ce, Fe, Mg, Mn, Zn) with no WHO guideline were also detected, with Mn the most common. This study demonstrated that filters and foams can be used for reconnaissance characterization of untreated drinking water. However, estimated metal and other analyte concentrations could only be reported as minimum values due to potential incomplete retrieval of foam-bound analytes. A qualitative reporting methodology was used to report analytes as "present" if the concentration was below the WHO guideline, and "present-recommend retesting" if the concentration was quantifiable and above the WHO guideline.

Diarrhea prevalence in a randomized, controlled prospective trial of point-of-use water filters in homes and schools in the Dominican Republic.

BACKGROUND: Lack of sustainable access to clean drinking water continues to be an issue of paramount global importance, leading to millions of preventable deaths annually. Best practices for providing sustainable access to clean drinking water, however, remain unclear. Widespread installation of low-cost, in-home, point of use water filtration systems is a promising strategy. METHODS: We conducted a prospective, randomized, controlled trial whereby 16 villages were selected and randomly assigned to one of four treatment arms based on the installation location of Sawyer® PointONE™ filters (filter in both home and school; filter in home only; filter in school only; control group). Water samples and self-reported information on diarrhea were collected at multiple times throughout the study. RESULTS: Self-reported household prevalence of diarrhea decreased from 25.6 to 9.76% from installation to follow-up (at least 7 days, and up to 200 days post-filter installation). These declines were also observed in diarrhea with economic or educational consequences (diarrhea which led to medical treatment and/or missing school or work) with baseline prevalence of 9.64% declining to 1.57%. Decreases in diarrhea prevalence were observed across age groups. There was no evidence of a loss of efficacy of filters up to 200 days post-filter installation. Installation of filters in schools was not associated with decreases in diarrhea prevalence in school-aged children or family members. Unfiltered water samples both at schools and homes contained potential waterborne bacterial pathogens, dissolved heavy metals and metals associated with particulates. All dissolved metals were detected at levels below World Health Organization action guidelines. CONCLUSIONS: This controlled trial provides strong evidence of the effectiveness of point-of-use, hollow fiber membrane filters at reducing diarrhea from bacterial sources up to 200 days post-installation when installed in homes. No statistically significant reduction in diarrhea was found when filters were installed in schools. Further research is needed in order to explore filter efficacy and utilization after 200 days post-installation. TRIAL REGISTRATION: ClinicalTrials.gov, NCT03972618 . Registered 3 June 2019-retrospectively registered.

Brain activation patterns in major depressive disorder and work stress-related long-term sick leave among Swedish females.

Deficits in executive functioning and working memory associated with frontal lobe dysfunction are prominent in depression and work-related long-term sick leave (LTSL). This study used functional magnetic resonance imaging (fMRI) to investigate potential differences in brain activation patterns in these conditions. In addition, the function of the hypothalamic-pituitary-adrenal (HPA) axis was examined and compared between groups. Since there is a clear overrepresentation of women in these diagnostic groups, and to ensure a more homogenous sample population, only women were included. To examine the neural correlates of relevant cognitive processes in patients on sick leave >90 days due to work-related LTSL, recently diagnosed patients with major depression Diagnostic and Statistical Manual of Mental Disorders, Fourth Edition (DSM-IV criteria, untreated), and healthy controls (n = 10, each group), a 2-back working memory task and a visual long-term memory task were administered during fMRI scanning. HPA axis functioning was investigated using a diurnal curve of saliva cortisol and a dexamethasone suppression test. Task performance was comparable among the three groups. Multivariate image analysis revealed that both memory tasks engaged a similar brain network in all three groups, including the prefrontal and parietal cortex. During the 2-back task, LTSL patients had significant frontal hypoactivation compared to controls and patients with depression. Saliva cortisol measurements showed a flattening of the diurnal rythmicity in LTSL patients compared to patients with depression and healthy contols. Taken together, these findings indicate that work stress-related LTSL and major depression are dissociable in terms of frontal activation and diurnal cortisol rhythmicity.

Cognitive deficits in relation to personality type and hypothalamic-pituitary-adrenal (HPA) axis dysfunction in women with stress-related exhaustion.

Exhaustion caused by long-term work-related stress may cause cognitive dysfunction. We explored factors that may link chronic stress and cognitive impairment. Personality, psychiatric screening, and behavior were assessed by self-reporting measures in 20 female patients (mean age 39.3 years; range 26-53) with a preliminary diagnosis of stress-related exhaustion and in 16 healthy matched controls. Cognitive performance was investigated with a detailed neuropsychological test battery. Cortisol axis function was assessed by urinary and saliva collections of cortisol, dexamethasone suppression, Synacthen response, and corticotropin-releasing hormone (CRH) tests. Proinflammatory cytokines were measured. Hippocampal volumes were estimated by magnetic resonance imaging. Multivariate and univariate statistical methods were used to explore putative differences between groups and factors linked to cognitive impairment. Cognitive function clearly differed between groups, with decreased attention and visuospatial memory in the patient group, suggesting frontal cortex/medial temporal cortex-network dysfunction. Increased harm avoidance and persistence was present among patients, with lowered self-directedness linked to lower quality of life, increased anxious and depressive tendencies, and experiences of psychosocial stress. Attention was decreased with concomitantly impaired visuospatial memory. The pituitary (adrenocorticotropic hormone, ACTH) response to CRH was decreased in patients, with an increased cortisol/ACTH response to CRH. However, cortisol production rates, diurnal or dexamethasone-suppressed saliva cortisol levels, and the cortisol response to Synacthen were unaltered. Hippocampal volumes did not differ between groups. These findings suggest that cognitive dysfunction in stress-related exhaustion is linked to distinct personality traits, low quality of life, and a decreased ACTH response to CRH.

Structural and functional consequences of missense mutations in exon 5 of the lipoprotein lipase gene.

Missense mutations in exon 5 of the LPL gene are the most common reported cause of LPL deficiency. Exon 5 is also the region with the strongest homology to pancreatic and hepatic lipase, and is conserved in LPL from different species. Mutant LPL proteins from post-heparin plasma from patients homozygous for missense mutations at amino acid positions 176, 188, 194, 205, and 207, and from COS cells transiently transfected with the corresponding cDNAs were quantified and characterized, in an attempt to determine which aspect of enzyme function was affected by each specific mutation. All but one of the mutant proteins were present, mainly as partially denatured LPL monomer, rendering further detailed assessment of their catalytic activity, affinity to heparin, and binding to lipoprotein particles difficult. However, the fresh unstable Gly(188)-->Glu LPL and the stable Ile(194)-->Thr LPL, although in native conformation, did not express lipase activity. It is proposed that many of the exon 5 mutant proteins are unable to achieve or maintain native dimer conformation, and that the Ile(194)-->Thr substitution interferes with access of lipid substrate to the catalytic pocket. These results stress the importance of conformational evaluation of mutant LPL. Absence of catalytic activity does not necessarily imply that the substituted amino acid plays a specific direct role in catalysis.