Enabling Oxidation Protection and Carrier-Type Switching for Bismuth Telluride Nanoribbons via in Situ Organic Molecule Coating.

Thermoelectric materials with high electrical conductivity and low thermal conductivity (e.g., Bi2Te3) can efficiently convert waste heat into electricity; however, in spite of favorable theoretical predictions, individual Bi2Te3 nanostructures tend to perform less efficiently than bulk Bi2Te3. We report a greater-than-order-of-magnitude enhancement in the thermoelectric properties of suspended Bi2Te3 nanoribbons, coated in situ to form a Bi2Te3/F4-TCNQ core-shell nanoribbon without oxidizing the core-shell interface. The shell serves as an oxidation barrier but also directly functions as a strong electron acceptor and p-type carrier donor, switching the majority carriers from a dominant n-type carrier concentration (∼1021 cm-3) to a dominant p-type carrier concentration (∼1020 cm-3). Compared to uncoated Bi2Te3 nanoribbons, our Bi2Te3/F4-TCNQ core-shell nanoribbon demonstrates an effective chemical potential dramatically shifted toward the valence band (by 300-640 meV), robustly increased Seebeck coefficient (∼6× at 250 K), and improved thermoelectric performance (10-20× at 250 K).

Coordinated regulation of the entry and exit steps of aromatic amino acid biosynthesis supports the dual lignin pathway in grasses.

Vascular plants direct large amounts of carbon to produce the aromatic amino acid phenylalanine to support the production of lignin and other phenylpropanoids. Uniquely, grasses, which include many major crops, can synthesize lignin and phenylpropanoids from both phenylalanine and tyrosine. However, how grasses regulate aromatic amino acid biosynthesis to feed this dual lignin pathway is unknown. Here we show, by stable-isotope labeling, that grasses produce tyrosine >10-times faster than Arabidopsis without compromising phenylalanine biosynthesis. Detailed in vitro enzyme characterization and combinatorial in planta expression uncovered that coordinated expression of specific enzyme isoforms at the entry and exit steps of the aromatic amino acid pathway enables grasses to maintain high production of both tyrosine and phenylalanine, the precursors of the dual lignin pathway. These findings highlight the complex regulation of plant aromatic amino acid biosynthesis and provide novel genetic tools to engineer the interface of primary and specialized metabolism in plants.

Evidence of a Uranium-Paddlewheel Node in a Catecholate-Based Metal-Organic Framework.

The interactions between uranium and non-innocent organic species are an essential component of fundamental uranium redox chemistry. However, they have seldom been explored in the context of multidimensional, porous materials. Uranium-based metal-organic frameworks (MOFs) offer a new angle to study these interactions, as these self-assembled species stabilize uranium species through immobilization by organic linkers within a crystalline framework, while potentially providing a method for adjusting metal oxidation state through coordination of non-innocent linkers. We report the synthesis of the MOF NU-1700, assembled from U4+ -paddlewheel nodes and catecholate-based linkers. We propose this highly unusual structure, which contains two U4+ ions in a paddlewheel built from four linkers-a first among uranium materials-as a result of extensive characterization via powder X-ray diffraction (PXRD), sorption, transmission electron microscopy (TEM), and thermogravimetric analysis (TGA), in addition to density functional theory (DFT) calculations.

Combating Fentanyl: National Guard Physician Assistants on the Front Lines of America's War Against Synthetic Opioids.

There is a significant threat to global health security due to synthetic opioids, illicitly manufactured fentanyl (IMF), and nefarious uses of pharmaceutical based agents (PBA). Since 2014, increased distribution of synthetic opioids including IMF into the US through China, India, and Mexico has resulted in devastating consequences to the average street drug user. Additionally, clandestine lab operations for pill manufacturing and distribution have increased, along with unintentional drug overdoses due to drugs being laced with fentanyl or some other synthetic opioid derivative. Naloxone has been shown to be an effective and useful tool for reversing signs and symptoms of synthetic opioid overdose, though additional doses may be required depending on the analog. In addition to the risk of overdose in US civilians, other state actors have utilized fentanyl and its analogs as incapacitants resulting in significant numbers of casualties. The National Guard Weapons of Mass Destruction-Civil Support Teams (WMD-CST) have been on the front lines supporting federal law enforcement agencies with hazard identification and assessment. Physician Assistants (PA) are assigned to these units and provide the necessary skills and expertise to keep on scene personnel safe. This article aims to dispel some of the rumors and myths surrounding fentanyl in an effort to educate first receivers, first responders, and hospital providers. Lastly, this article provides a review of synthetic opioid production, overdose, hazards, treatment/countermeasures, decontamination for responders, and the potential use of synthetic opioids as WMDs.

Polymer networks of imine-crosslinked metal-organic cages: tuneable viscoelasticity and iodine adsorption.

The solution-state structure of an amine-functionalised Cu24L24 cage (MOP-15) is elucidated, enabling its direct covalent crosslinking into a series of highly tuneable organogels. These soft porous networks exhibit up to a ∼10-fold increase in capacity for iodine compared to the discrete cage precursor.

Induced Ferromagnetism in Epitaxial Uranium Dioxide Thin Films.

Actinide materials have various applications that range from nuclear energy to quantum computing. Most current efforts have focused on bulk actinide materials. Tuning functional properties by using strain engineering in epitaxial thin films is largely lacking. Using uranium dioxide (UO2 ) as a model system, in this work, the authors explore strain engineering in actinide epitaxial thin films and investigate the origin of induced ferromagnetism in an antiferromagnet UO2 . It is found that UO2+ x thin films are hypostoichiometric (x<0) with in-plane tensile strain, while they are hyperstoichiometric (x>0) with in-plane compressive strain. Different from strain engineering in non-actinide oxide thin films, the epitaxial strain in UO2 is accommodated by point defects such as vacancies and interstitials due to the low formation energy. Both epitaxial strain and strain relaxation induced point defects such as oxygen/uranium vacancies and oxygen/uranium interstitials can distort magnetic structure and result in magnetic moments. This work reveals the correlation among strain, point defects and ferromagnetism in strain engineered UO2+ x thin films and the results offer new opportunities to understand the influence of coupled order parameters on the emergent properties of many other actinide thin films.

Patient-, Hospital-, and System-Level Factors Associated With 30-Day Readmission After a Psychiatric Hospitalization.

ABSTRACT: Readmission after inpatient care for a psychiatric condition is associated with a range of adverse events including suicide and all-cause mortality. This study estimated 30-day readmission rates in a large cohort of inpatient psychiatric admissions in New York State and examined how these rates varied by patient, hospital, and service system characteristics. Data were obtained from Medicaid claims records, and clinician, hospital, and region data, for individuals with a diagnosis of any mental disorder admitted to psychiatric inpatient units in New York State from 2012 to 2013. Psychiatric readmission was defined as any unplanned inpatient stay with a mental health diagnosis with an admission date within 30 days of being discharged. Unadjusted and adjusted odds ratios of being readmitted within 30 days were estimated using logistic regression analyses. Over 15% of individuals discharged from inpatient units between 2012 and 2013 were readmitted within 30 days. Patients who were readmitted were more likely to be homeless, have a schizoaffective disorder or schizophrenia, and have medical comorbidity. Readmission rates varied in this cohort mainly because of individual-level characteristics. Homeless patients were at the highest risk of being readmitted after discharge.

Visualizing Grain Statistics in MOCVD WSe2 through Four-Dimensional Scanning Transmission Electron Microscopy.

Using four-dimensional scanning transmission electron microscopy, we demonstrate a method to visualize grains and grain boundaries in WSe2 grown by metal organic chemical vapor deposition (MOCVD) directly onto silicon dioxide. Despite the chemical purity and uniform thickness and texture of the MOCVD-grown WSe2, we observe a high density of small grains that corresponds with the overall selenium deficiency we measure through ion beam analysis. Moreover, reconstruction of grain information permits the creation of orientation maps that demonstrate the nucleation mechanism for new layers-triangular domains with the same orientation as the layer underneath induces a tensile strain increasing the lattice parameter at these sites.

The Effectiveness of Discharge Planning for Psychiatric Inpatients With Varying Levels of Preadmission Engagement in Care.

OBJECTIVE: This study examined the extent to which prehospital treatment engagement is related to posthospital follow-up treatment among psychiatric inpatients and whether the effects of inpatient discharge planning on posthospital follow-up treatment vary by level of pretreatment engagement in care. METHODS: New York State Medicaid and other administrative databases were used to examine service use by 18,793 adult patients discharged to the community after inpatient psychiatric care in 2012-2013. Outcomes included attending an outpatient mental health service within 7 days and within 30 days after discharge. The sample was stratified by whether patients had high, partial, low, or no engagement in outpatient psychiatric services in the 6 months before admission. RESULTS: Scheduling an outpatient appointment as part of the patient's discharge plan was significantly associated with attending outpatient psychiatric appointments, regardless of the patient's level of engagement in care before admission. The differences were most pronounced for patients who had not received any outpatient care in the 6 months before admission. When an appointment was scheduled, these patients were three times more likely to follow up with care within 7 days and more than twice as likely to follow up within 30 days than were patients without a scheduled appointment. CONCLUSIONS: The likelihood of psychiatric inpatients following up with outpatient psychiatric care was directly related to their level of outpatient care engagement before hospital admission. Even among those who had not been engaged in outpatient care, inpatient discharge planning was associated with a greater likelihood of receiving follow-up outpatient care.

Use of predictive models to identify patients who are likely to benefit from refraction at a follow-up visit after cataract surgery.

PURPOSE: To develop predictive models to identify cataract surgery patients who are more likely to benefit from refraction at a four-week postoperative exam. METHODS: In this retrospective study, we used data of all 86,776 cataract surgeries performed in 2015 at a large tertiary-care eye hospital in India. The outcome variable was a binary indicator of whether the difference between corrected distance visual acuity and uncorrected visual acuity at the four-week postoperative exam was at least two lines on the Snellen chart. We examined the following statistical models: logistic regression, decision tree, pruned decision tree, random forest, weighted k-nearest neighbor, and a neural network. Predictor variables included in each model were patient sex and age, source eye (left or right), preoperative visual acuity, first-day postoperative visual acuity, intraoperative and immediate postoperative complications, and combined surgeries. We compared the predictive performance of models and assessed their clinical impact in test samples. RESULTS: All models demonstrated predictive accuracy better than chance based on area under the receiver operating characteristic curve. In a targeting exercise with a fixed intervention budget, we found that gains from predictive models in identifying patients who would benefit from refraction ranged from 7.8% (increase from 1500 to 1617 patients) to 74% (increase from 250 to 435 patients). CONCLUSION: The use of predictive statistical models to identify patients who are likely to benefit from refraction at follow-up can improve the economic efficiency of interventions. Simpler models like logistic regression perform almost as well as more complex machine-learning models, but are easier to implement.

Trends and outcomes in primary health care expenditures in low-income and middle-income countries, 2000-2017.

INTRODUCTION: As the world responds to COVID-19 and aims for the Sustainable Development Goals, the potential for primary healthcare (PHC) is substantial, although the trends and effectiveness of PHC expenditure are unknown. We estimate PHC expenditure for each low-income and middle-income country between 2000 and 2017 and test which health outputs and outcomes were associated with PHC expenditure. METHODS: We used three data sources to estimate PHC expenditures: recently published health expenditure estimates for each low-income and middle-income country, which were constructed using 1662 country-reported National Health Accounts; proprietary data from IQVIA to estimate expenditure of prescribed pharmaceuticals for PHC; and household surveys and costing estimates to estimate inpatient vaginal delivery expenditures. We employed regression analyses to measure the association between PHC expenditures and 15 health outcomes and intermediate health outputs. RESULTS: PHC expenditures in low-income and middle-income countries increased between 2000 and 2017, from $41 per capita (95% uncertainty interval $33-$49) to $90 ($73-$105). Expenditures for low-income countries plateaued since 2014 at $17 per capita ($15-$19). As national income increased, the proportion of health expenditures on PHC generally decrease; however, the fraction of PHC expenditures spent via ambulatory care providers grew. Increases in the fraction of health expenditures on PHC was associated with lower maternal mortality rate (p value≤0.001), improved coverage of antenatal care visits (p value≤0.001), measles vaccination (p value≤0.001) and an increase in the Health Access and Quality index (p value≤0.05). PHC expenditure was not systematically associated with all-age mortality, communicable and non-communicable disease (NCD) burden. CONCLUSION: PHC expenditures were associated with maternal and child health but were not associated with reduction in health burden for other key causes of disability, such as NCDs. To combat changing disease burdens, policy-makers and health professionals need to adapt primary healthcare to ensure continued impact on emerging health challenges.

Health expenditures by services and providers for 195 countries, 2000-2017.

INTRODUCTION: National Health Accounts are a significant source of health expenditure data, designed to be comprehensive and comparable across countries. However, there is currently no single repository of this data and even when compiled major gaps persist. This research aims to provide policymakers and researchers with a single repository of available national health expenditures by healthcare functions (ie, services) and providers of such services. Leveraging these data within statistical methods, a complete set of detailed health expenditures is estimated. METHODS: A methodical compilation and synthesis of all available national health expenditure reports including disaggregation by healthcare functions and providers was conducted. Using these data, a Bayesian multivariate regression analysis was implemented to estimate national-level health expenditures by the cross-classification of functions and providers for 195 countries, from 2000 to 2017. RESULTS: This research used 1662 country-years and 110 070 data points of health expenditures from existing National Health Accounts. The most detailed country-year had 52% of the categories of interest reported. Of all health functions, curative care and medical goods were estimated to make up 51.4% (uncertainty interval (UI) 33.2% to 59.4%) and 17.5% (UI 13.0% to 26.9%) of total global health expenditures in 2017, respectively. Three-quarters of the global health expenditures are allocated to three categories of providers: hospital providers (35.4%, UI 30.3% to 38.9%), providers of ambulatory care (25.5%, UI 21.1% to 28.8%) and retailers of medical goods (14.4%, UI 12.4% to 16.3%). As gross domestic product increases, countries spend more on long-term care and less on preventive care. CONCLUSION: Disaggregated estimates of health expenditures are often unavailable and unable to provide policymakers and researchers a holistic understanding of how expenditures are used. This research aggregates reported data and provides a complete time-series of estimates, with uncertainty, of health expenditures by health functions and providers between 2000 and 2017 for 195 countries.

Assembly and Covalent Cross-Linking of an Amine-Functionalised Metal-Organic Cage.

The incorporation of reactive functional groups onto the exterior of metal-organic cages (MOCs) opens up new opportunities to link their well-defined scaffolds into functional porous solids. Amine moieties offer access to a rich catalogue of covalent chemistry; however, they also tend to coordinate undesirably and interfere with MOC formation, particular in the case of Cu2 paddlewheel-based MOCs. We demonstrate that tuning the basicity of an aniline-functionalized ligand enables the self-assembly of a soluble, amine-functionalized Cu4L4 lantern cage (1). Importantly, we show control over the coordinative propensity of the exterior amine of the ligand, which enables us to isolate a crystalline, two-dimensional metal-organic framework composed entirely of MOC units (2). Furthermore, we show that the nucleophilicity of the exterior amine of 1 can be accessed in solution to generate a cross-linked cage polymer (3) via imine condensation.

Intrinsic helical twist and chirality in ultrathin tellurium nanowires.

Robust atomic-to-meso-scale chirality is now observed in the one-dimensional form of tellurium. This enables a large and counter-intuitive circular-polarization dependent second harmonic generation response above 0.2 which is not present in two-dimensional tellurium. Orientation variations in 1D tellurium nanowires obtained by four-dimensional scanning transmission electron microscopy (4D-STEM) and their correlation with unconventional non-linear optical properties by second harmonic generation circular dichroism (SHG-CD) uncovers an unexpected circular-polarization dependent SHG response from 1D nanowire bundles - an order-of-magnitude higher than in single-crystal two-dimensional tellurium structures - suggesting the atomic- and meso-scale crystalline structure of the 1D material possesses an inherent chirality not present in its 2D form; and which is strong enough to manifest even in the aggregate non-linear optical (NLO) properties of aggregates.

py4DSTEM: A Software Package for Four-Dimensional Scanning Transmission Electron Microscopy Data Analysis.

Scanning transmission electron microscopy (STEM) allows for imaging, diffraction, and spectroscopy of materials on length scales ranging from microns to atoms. By using a high-speed, direct electron detector, it is now possible to record a full two-dimensional (2D) image of the diffracted electron beam at each probe position, typically a 2D grid of probe positions. These 4D-STEM datasets are rich in information, including signatures of the local structure, orientation, deformation, electromagnetic fields, and other sample-dependent properties. However, extracting this information requires complex analysis pipelines that include data wrangling, calibration, analysis, and visualization, all while maintaining robustness against imaging distortions and artifacts. In this paper, we present py4DSTEM, an analysis toolkit for measuring material properties from 4D-STEM datasets, written in the Python language and released with an open-source license. We describe the algorithmic steps for dataset calibration and various 4D-STEM property measurements in detail and present results from several experimental datasets. We also implement a simple and universal file format appropriate for electron microscopy data in py4DSTEM, which uses the open-source HDF5 standard. We hope this tool will benefit the research community and help improve the standards for data and computational methods in electron microscopy, and we invite the community to contribute to this ongoing project.

Factors Associated With Discharge Planning Practices for Patients Receiving Inpatient Psychiatric Care.

OBJECTIVE: This study examined associations of patient, hospital, and service system factors with provision of discharge planning to individuals treated in hospital psychiatric units. METHODS: This retrospective cohort analysis used 2012-2013 New York State Medicaid claims data of 18,185 patients ages <65 years who were treated in hospital psychiatric units and discharged to the community. The claims data were linked to data from managed behavioral health care organizations indicating whether inpatient staff scheduled a follow-up outpatient appointment with a mental health provider. Additional data regarding hospital and service system characteristics were obtained from the American Hospital Association Annual Survey, the Area Health Resource File, and other state administrative databases. Rates and adjusted odds ratios were assessed for the likelihood of inpatient staff scheduling a follow-up appointment. RESULTS: Inpatient staff scheduled outpatient appointments for 79.8% of discharges. The adjusted odds of not having an outpatient appointment scheduled as part of the patient's discharge plan were significantly associated with several factors, including being homeless on admission, having a diagnosis of a co-occurring substance use disorder, having high levels of medical comorbid conditions, and not being engaged in psychiatric outpatient services in the month prior to admission. CONCLUSIONS: Patient characteristics were more strongly associated with failure to receive discharge planning than were hospital and service system characteristics.

Self-sorting of porous Cu4L2L'2 metal-organic cages composed of isomerisable ligands.

We report the self-sorting of a dynamic combinatorial library (DCL) of metal-organic cages composed of a rotationally isomerisable ligand. Convergence of the DCL occurs upon crystallisation and leads to low-symmetry Cu4L2L'2 cages that display differing porosities based on their overall shape and ligand configuration.