Synthesis and Characterization of Novel Metal-Oxo Clusters as the Building Blocks in Nature and Synthesis

Metal-oxo clusters can be described as soluble pieces of metal-oxide frameworks. Metal-oxo clusters are also the building blocks for the Metal-Organic Frameworks (MOFs) and coordination polymers. A better knowledge of metal-oxo clusters helps fundamentally understand geosciences, molecular engineering, catalysis, single-molecule magnetism, and MOFs for synthesis, design, and modification of these materials. This dissertation aims to demonstrate the synthesis of different metal-oxo clusters and monitor the reaction pathway with analytical techniques. We control the reactions to isolate the desired metal-oxo clusters and study their aggregation the form metal oxides, metal-oxo networks, and coordination polymers. Based on the nature of metal ions, the metal-oxo cluster forms as negative or positive charge molecules named polyoxoanion and polyoxocation. There have been a lot of studies on metal-oxo clusters; however, investigating all types of metal-oxo clusters and their potential for extended coordination structure hasn't been done best of our knowledge. Herein we study Nb-oxo clusters as an example of negatively charged metal-oxo clusters and use carbonate ligand to extend the Nb10-CO3 structure to a two-dimensional coordination network. In a further study on Nb chemistry, we replaced some Nb-oxo unites with lanthanides to explore these structures. This study isolated five structures with Nb-based polyoxometalate coordinated with carbonate ligands

A 21-year-old Pregnant Trauma Patient with Asymptomatic Fat Embolism; a Case Report

Introduction: Fat embolism syndrome (FES) is most often associated with orthopedic trauma that typically presents 24–72 hours after the trauma with a classic triad. Only few cases of fat embolism due to lower extremity venous system had been reported. Case presentation: The current case report presents a pregnant woman who was referred to our emergency department with bilateral femoral open fracture. After detecting fetal demise by abdominopelvic ultrasound, an area of fat density in right external iliac vein was detected in abdominopelvic contrast enhanced computed tomography (CT) scan which was considered as the probable diagnosis of fat embolism. While the patient did not show signs and symptoms of FES, the fat embolism was confirmed in further evaluations. Conclusion: In summary, although detection of fat embolus in CT scan in the emergency department is very rare, evaluation of lower extremity venous system in a posttraumatic patient seems to be crucial because early diagnosis of fat embolism can help the clinicians to prevent FES

A 21-year-old Pregnant Trauma Patient with Asymptomatic Fat Embolism; a Case Report

Introduction: Fat embolism syndrome (FES) is most often associated with orthopedic trauma that typically presents 24–72 hours after the trauma with a classic triad. Only few cases of fat embolism due to lower extremity venous system had been reported. Case presentation: The current case report presents a pregnant woman who was referred to our emergency department with bilateral femoral open fracture. After detecting fetal demise by abdominopelvic ultrasound, an area of fat density in right external iliac vein was detected in abdominopelvic contrast enhanced computed tomography (CT) scan which was considered as the probable diagnosis of fat embolism. While the patient did not show signs and symptoms of FES, the fat embolism was confirmed in further evaluations. Conclusion: In summary, although detection of fat embolus in CT scan in the emergency department is very rare, evaluation of lower extremity venous system in a posttraumatic patient seems to be crucial because early diagnosis of fat embolism can help the clinicians to prevent FES

Atomically-precise lanthanide-iron-oxo clusters featuring the ε-Keggin ion.

Atomically precise molecular metal-oxo clusters provide ideal models to understand metal oxide surfaces, self-assembly, and form-function relationships. Devising strategies for synthesis and isolation of these molecular forms remains a challenge. Here, we report the synthesis of four Ln-Fe oxo clusters that feature the ε -{Fe 13 } Keggin cluster in its core. The {Fe 13 } metal-oxo cluster motif is the building block of two important iron oxyhydroxyide phases in nature and technology, ferrihydrite (as the δ -isomer) and magnetite (the ε -isomer). The reported ε -{Fe 13 } Keggin isomer as an isolated molecule provides opportunity to study the formation of ferrihydrite and magnetite from this building unit. The next metal layer surrounding the ε -{Fe 13 } core within these clusters exhibit a similar arrangement as the magnetite lattice, and Fe and Ln can occupy the same positions. This provides opportunity to construct a family of compounds and optimize magnetic exchange in these molecules via composition tuning. Small angle X-ray scattering (SAXS) and high-resolution electrospray ionization mass spectrometry (HRESI-MS) show these clusters are stable upon dissolution in both water and organic solvents, as a first step to perform further chemistry towards building magnetic arrays or invetigating ferrihydrite and magnetite assembly from pre-nucleation clusters

Measuring universal health coverage based on an index of effective coverage of health services in 204 countries and territories, 1990–2019: a systematic analysis for the Global Burden of Disease Study 2019

© 2020 Author(s). Published by Elsevier Ltd. This is an Open Access article under the CC BY 4.0 license Background: Achieving universal health coverage (UHC) involves all people receiving the health services they need, of high quality, without experiencing financial hardship. Making progress towards UHC is a policy priority for both countries and global institutions, as highlighted by the agenda of the UN Sustainable Development Goals (SDGs) and WHO's Thirteenth General Programme of Work (GPW13). Measuring effective coverage at the health-system level is important for understanding whether health services are aligned with countries' health profiles and are of sufficient quality to produce health gains for populations of all ages. Methods: Based on the Global Burden of Diseases, Injuries, and Risk Factors Study (GBD) 2019, we assessed UHC effective coverage for 204 countries and territories from 1990 to 2019. Drawing from a measurement framework developed through WHO's GPW13 consultation, we mapped 23 effective coverage indicators to a matrix representing health service types (eg, promotion, prevention, and treatment) and five population-age groups spanning from reproductive and newborn to older adults (≥65 years). Effective coverage indicators were based on intervention coverage or outcome-based measures such as mortality-to-incidence ratios to approximate access to quality care; outcome-based measures were transformed to values on a scale of 0–100 based on the 2·5th and 97·5th percentile of location-year values. We constructed the UHC effective coverage index by weighting each effective coverage indicator relative to its associated potential health gains, as measured by disability-adjusted life-years for each location-year and population-age group. For three tests of validity (content, known-groups, and convergent), UHC effective coverage index performance was generally better than that of other UHC service coverage indices from WHO (ie, the current metric for SDG indicator 3.8.1 on UHC service coverage), the World Bank, and GBD 2017. We quantified frontiers of UHC effective coverage performance on the basis of pooled health spending per capita, representing UHC effective coverage index levels achieved in 2019 relative to country-level government health spending, prepaid private expenditures, and development assistance for health. To assess current trajectories towards the GPW13 UHC billion target—1 billion more people benefiting from UHC by 2023—we estimated additional population equivalents with UHC effective coverage from 2018 to 2023. Findings: Globally, performance on the UHC effective coverage index improved from 45·8 (95% uncertainty interval 44·2–47·5) in 1990 to 60·3 (58·7–61·9) in 2019, yet country-level UHC effective coverage in 2019 still spanned from 95 or higher in Japan and Iceland to lower than 25 in Somalia and the Central African Republic. Since 2010, sub-Saharan Africa showed accelerated gains on the UHC effective coverage index (at an average increase of 2·6% [1·9–3·3] per year up to 2019); by contrast, most other GBD super-regions had slowed rates of progress in 2010–2019 relative to 1990–2010. Many countries showed lagging performance on effective coverage indicators for non-communicable diseases relative to those for communicable diseases and maternal and child health, despite non-communicable diseases accounting for a greater proportion of potential health gains in 2019, suggesting that many health systems are not keeping pace with the rising non-communicable disease burden and associated population health needs. In 2019, the UHC effective coverage index was associated with pooled health spending per capita (r=0·79), although countries across the development spectrum had much lower UHC effective coverage than is potentially achievable relative to their health spending. Under maximum efficiency of translating health spending into UHC effective coverage performance, countries would need to reach $1398 pooled health spending per capita (US$ adjusted for purchasing power parity) in order to achieve 80 on the UHC effective coverage index. From 2018 to 2023, an estimated 388·9 million (358·6–421·3) more population equivalents would have UHC effective coverage, falling well short of the GPW13 target of 1 billion more people benefiting from UHC during this time. Current projections point to an estimated 3·1 billion (3·0–3·2) population equivalents still lacking UHC effective coverage in 2023, with nearly a third (968·1 million [903·5–1040·3]) residing in south Asia. Interpretation: The present study demonstrates the utility of measuring effective coverage and its role in supporting improved health outcomes for all people—the ultimate goal of UHC and its achievement. Global ambitions to accelerate progress on UHC service coverage are increasingly unlikely unless concerted action on non-communicable diseases occurs and countries can better translate health spending into improved performance. Focusing on effective coverage and accounting for the world's evolving health needs lays the groundwork for better understanding how close—or how far—all populations are in benefiting from UHC. Funding: Bill & Melinda Gates Foundation

The unfinished agenda of communicable diseases among children and adolescents before the COVID-19 pandemic, 1990-2019: a systematic analysis of the Global Burden of Disease Study 2019

BACKGROUND: Communicable disease control has long been a focus of global health policy. There have been substantial reductions in the burden and mortality of communicable diseases among children younger than 5 years, but we know less about this burden in older children and adolescents, and it is unclear whether current programmes and policies remain aligned with targets for intervention. This knowledge is especially important for policy and programmes in the context of the COVID-19 pandemic. We aimed to use the Global Burden of Disease (GBD) Study 2019 to systematically characterise the burden of communicable diseases across childhood and adolescence. METHODS: In this systematic analysis of the GBD study from 1990 to 2019, all communicable diseases and their manifestations as modelled within GBD 2019 were included, categorised as 16 subgroups of common diseases or presentations. Data were reported for absolute count, prevalence, and incidence across measures of cause-specific mortality (deaths and years of life lost), disability (years lived with disability [YLDs]), and disease burden (disability-adjusted life-years [DALYs]) for children and adolescents aged 0-24 years. Data were reported across the Socio-demographic Index (SDI) and across time (1990-2019), and for 204 countries and territories. For HIV, we reported the mortality-to-incidence ratio (MIR) as a measure of health system performance. FINDINGS: In 2019, there were 3·0 million deaths and 30·0 million years of healthy life lost to disability (as measured by YLDs), corresponding to 288·4 million DALYs from communicable diseases among children and adolescents globally (57·3% of total communicable disease burden across all ages). Over time, there has been a shift in communicable disease burden from young children to older children and adolescents (largely driven by the considerable reductions in children younger than 5 years and slower progress elsewhere), although children younger than 5 years still accounted for most of the communicable disease burden in 2019. Disease burden and mortality were predominantly in low-SDI settings, with high and high-middle SDI settings also having an appreciable burden of communicable disease morbidity (4·0 million YLDs in 2019 alone). Three cause groups (enteric infections, lower-respiratory-tract infections, and malaria) accounted for 59·8% of the global communicable disease burden in children and adolescents, with tuberculosis and HIV both emerging as important causes during adolescence. HIV was the only cause for which disease burden increased over time, particularly in children and adolescents older than 5 years, and especially in females. Excess MIRs for HIV were observed for males aged 15-19 years in low-SDI settings. INTERPRETATION: Our analysis supports continued policy focus on enteric infections and lower-respiratory-tract infections, with orientation to children younger than 5 years in settings of low socioeconomic development. However, efforts should also be targeted to other conditions, particularly HIV, given its increased burden in older children and adolescents. Older children and adolescents also experience a large burden of communicable disease, further highlighting the need for efforts to extend beyond the first 5 years of life. Our analysis also identified substantial morbidity caused by communicable diseases affecting child and adolescent health across the world. FUNDING: The Australian National Health and Medical Research Council Centre for Research Excellence for Driving Investment in Global Adolescent Health and the Bill & Melinda Gates Foundation

Mapping development and health effects of cooking with solid fuels in low-income and middle-income countries, 2000-18 : a geospatial modelling study

Background More than 3 billion people do not have access to clean energy and primarily use solid fuels to cook. Use of solid fuels generates household air pollution, which was associated with more than 2 million deaths in 2019. Although local patterns in cooking vary systematically, subnational trends in use of solid fuels have yet to be comprehensively analysed. We estimated the prevalence of solid-fuel use with high spatial resolution to explore subnational inequalities, assess local progress, and assess the effects on health in low-income and middle-income countries (LMICs) without universal access to clean fuels.Methods We did a geospatial modelling study to map the prevalence of solid-fuel use for cooking at a 5 km x 5 km resolution in 98 LMICs based on 2.1 million household observations of the primary cooking fuel used from 663 population-based household surveys over the years 2000 to 2018. We use observed temporal patterns to forecast household air pollution in 2030 and to assess the probability of attaining the Sustainable Development Goal (SDG) target indicator for clean cooking. We aligned our estimates of household air pollution to geospatial estimates of ambient air pollution to establish the risk transition occurring in LMICs. Finally, we quantified the effect of residual primary solid-fuel use for cooking on child health by doing a counterfactual risk assessment to estimate the proportion of deaths from lower respiratory tract infections in children younger than 5 years that could be associated with household air pollution.Findings Although primary reliance on solid-fuel use for cooking has declined globally, it remains widespread. 593 million people live in districts where the prevalence of solid-fuel use for cooking exceeds 95%. 66% of people in LMICs live in districts that are not on track to meet the SDG target for universal access to clean energy by 2030. Household air pollution continues to be a major contributor to particulate exposure in LMICs, and rising ambient air pollution is undermining potential gains from reductions in the prevalence of solid-fuel use for cooking in many countries. We estimated that, in 2018, 205000 (95% uncertainty interval 147000-257000) children younger than 5 years died from lower respiratory tract infections that could be attributed to household air pollution.Interpretation Efforts to accelerate the adoption of clean cooking fuels need to be substantially increased and recalibrated to account for subnational inequalities, because there are substantial opportunities to improve air quality and avert child mortality associated with household air pollution. Copyright (C) 2022 The Author(s). Published by Elsevier Ltd.Peer reviewe

Mapping local patterns of childhood overweight and wasting in low- and middle-income countries between 2000 and 2017

A double burden of malnutrition occurs when individuals, household members or communities experience both undernutrition and overweight. Here, we show geospatial estimates of overweight and wasting prevalence among children under 5 years of age in 105 low- and middle-income countries (LMICs) from 2000 to 2017 and aggregate these to policy-relevant administrative units. Wasting decreased overall across LMICs between 2000 and 2017, from 8.4% (62.3 (55.1–70.8) million) to 6.4% (58.3 (47.6–70.7) million), but is predicted to remain above the World Health Organization’s Global Nutrition Target of <5% in over half of LMICs by 2025. Prevalence of overweight increased from 5.2% (30 (22.8–38.5) million) in 2000 to 6.0% (55.5 (44.8–67.9) million) children aged under 5 years in 2017. Areas most affected by double burden of malnutrition were located in Indonesia, Thailand, southeastern China, Botswana, Cameroon and central Nigeria. Our estimates provide a new perspective to researchers, policy makers and public health agencies in their efforts to address this global childhood syndemic