Global, regional, and national progress towards Sustainable Development Goal 3.2 for neonatal and child health: all-cause and cause-specific mortality findings from the Global Burden of Disease Study 2019

Background Sustainable Development Goal 3.2 has targeted elimination of preventable child mortality, reduction of neonatal death to less than 12 per 1000 livebirths, and reduction of death of children younger than 5 years to less than 25 per 1000 livebirths, for each country by 2030. To understand current rates, recent trends, and potential trajectories of child mortality for the next decade, we present the Global Burden of Diseases, Injuries, and Risk Factors Study (GBD) 2019 findings for all-cause mortality and cause-specific mortality in children younger than 5 years of age, with multiple scenarios for child mortality in 2030 that include the consideration of potential effects of COVID-19, and a novel framework for quantifying optimal child survival. Methods We completed all-cause mortality and cause-specific mortality analyses from 204 countries and territories for detailed age groups separately, with aggregated mortality probabilities per 1000 livebirths computed for neonatal mortality rate (NMR) and under-5 mortality rate (USMR). Scenarios for 2030 represent different potential trajectories, notably including potential effects of the COVID-19 pandemic and the potential impact of improvements preferentially targeting neonatal survival. Optimal child survival metrics were developed by age, sex, and cause of death across all GBD location-years. The first metric is a global optimum and is based on the lowest observed mortality, and the second is a survival potential frontier that is based on stochastic frontier analysis of observed mortality and Healthcare Access and Quality Index. Findings Global U5MR decreased from 71.2 deaths per 1000 livebirths (95% uncertainty interval WI] 68.3-74-0) in 2000 to 37.1 (33.2-41.7) in 2019 while global NMR correspondingly declined more slowly from 28.0 deaths per 1000 live births (26.8-29-5) in 2000 to 17.9 (16.3-19-8) in 2019. In 2019,136 (67%) of 204 countries had a USMR at or below the SDG 3.2 threshold and 133 (65%) had an NMR at or below the SDG 3.2 threshold, and the reference scenario suggests that by 2030,154 (75%) of all countries could meet the U5MR targets, and 139 (68%) could meet the NMR targets. Deaths of children younger than 5 years totalled 9.65 million (95% UI 9.05-10.30) in 2000 and 5.05 million (4.27-6.02) in 2019, with the neonatal fraction of these deaths increasing from 39% (3.76 million 95% UI 3.53-4.021) in 2000 to 48% (2.42 million; 2.06-2.86) in 2019. NMR and U5MR were generally higher in males than in females, although there was no statistically significant difference at the global level. Neonatal disorders remained the leading cause of death in children younger than 5 years in 2019, followed by lower respiratory infections, diarrhoeal diseases, congenital birth defects, and malaria. The global optimum analysis suggests NMR could be reduced to as low as 0.80 (95% UI 0.71-0.86) deaths per 1000 livebirths and U5MR to 1.44 (95% UI 1-27-1.58) deaths per 1000 livebirths, and in 2019, there were as many as 1.87 million (95% UI 1-35-2.58; 37% 95% UI 32-43]) of 5.05 million more deaths of children younger than 5 years than the survival potential frontier. Interpretation Global child mortality declined by almost half between 2000 and 2019, but progress remains slower in neonates and 65 (32%) of 204 countries, mostly in sub-Saharan Africa and south Asia, are not on track to meet either SDG 3.2 target by 2030. Focused improvements in perinatal and newborn care, continued and expanded delivery of essential interventions such as vaccination and infection prevention, an enhanced focus on equity, continued focus on poverty reduction and education, and investment in strengthening health systems across the development spectrum have the potential to substantially improve USMR. Given the widespread effects of COVID-19, considerable effort will be required to maintain and accelerate progress. Copyright (C) 2021 The Author(s). Published by Elsevier Ltd

New metal catalyzed syntheses of nanostructured boron nitride and alkenyldecaboranes

The goals of the research described in this dissertation were two-fold. The first goal was to develop new methods, employing metal-catalyzed chemical vapor deposition reactions of molecular polyborane precursors, for the production of boron nitride nanostructured materials, including both boron nitride nanotubes (BNNTs) and boron nitride nanosheets (BNNS). The second goal was to develop new systematic metal-catalyzed reactions for polyboranes that would facilitate their functionalization for possible biomedical and/or materials applications. The syntheses of multi- and double-walled BNNTs were achieved with the aid of a floating nickel catalyst via the catalytic chemical vapor deposition (CCVD) of borazine (B3N3H6) or decaborane (B10H14) molecular precursors in ammonia atmospheres, with each precursor having its own advantages. While borazine is a single-source precursor containing both boron and nitrogen, the decaborane-based syntheses required the additional step of reaction with ammonia. However, the higher observed BNNT yields and the ease of handling and commercial availability of decaborane are distinct advantages. The BNNTs derived from both precursors were crystalline with highly ordered structures. The BNNTs grown at 1200 ºC from borazine were mainly double walled, with lengths up to 0.2 µm and ∼2 nm diameters. The BNNTs grown at 1200–1300 ºC from decaborane were double- and multi-walled, with the double-walled nanotubes having ∼2 nm inner diameters and the multi-walled nanotubes (∼10 walls) having ∼4–5 nm inner diameters and ∼12–14 nm outer diameters. BNNTs grown from decaborane at 1300 ºC were longer, averaging ∼0.6 µm, whereas those grown at 1200 ºC had average lengths of ∼0.2 µm. The BNNTs were characterized using scanning and transmission electron microscopies (SEM and TEM), and electron energy loss spectroscopy (EELS). This floating catalyst method now provides a catalytic and potentially scalable route to BNNTs with low defect density from safe and commercially available precursor compounds. A catalytic CVD method, employing the thermally induced reactions of ammonia with decaborane on polycrystalline nickel and copper foils, was also successfully developed for the production of BNNS. The metals were readily etched and the BNNS transferred to other substrates. The EELS and Raman spectra and the electron diffraction patterns of the BNNS confirmed the formation of h-BN and their optical, AFM and TEM characterizations showed BNNS with large micron-scale areas with some crumpling and folding. Most of the BNNS deposited on Ni were two- or three-layered; however, some regions were thicker containing up to six BN sheets. The films on Cu also contained two- and three-layered BNNS, but had large amorphous BN regions. Many of the BNNS grown on Ni exhibited well-defined angular edges, with near regular angles of 30º, 60º or 90º, suggesting that with a fine-tuning of the decaborane/ammonia pressure and growth conditions, controlled growth of regular polygonal BNNS structures can be achieved. To achieve the second goal, transition-metal-catalyzed decaborane-alkyne hydroboration reactions were developed that provide high-yield routes to the previously unknown di- and monoalkenyldecaboranes. An unusual catalyst product selectivity was observed, with the reactions catalyzed by the [RuCl2 (p-cymene)]2 and [Cp*IrCl2]2 complexes giving the β-E alkenyldecaboranes and the corresponding reactions with the [RuI2(p-cymene)]2 complex giving the α-alkenyldecaborane isomers. These product selectivities coupled with the differences observed in NMR studies of catalyzed reactions in progress, suggest quite distinct mechanistic steps for the different catalysts. It was further demonstrated that the new alkenyldecaboranes could be easily modified with the aid of metal-catalyzed hydroborations and homo and cross metathesis reactions to yield both linked cage and chemically active derivatives. These results demonstrate that the alkenyldecaboranes could serve as important materials for many potential polyborane biomedical and/or materials applications

Acute Intestinal Obstruction: A Rare Aetiology

Internal herniation of small intestine is a very rare entity, and it poses a real diagnostic challenge clinically. Recurrent entrapment of the bowel may lead to partial to complete intestinal obstruction and eventually strangulation of the small bowel. Of this rare clinical entity, left paraduodenal hernia is more common. High index of suspicion with prompt management may prevent bowel strangulation and gangrene. We present a case of acute intestinal obstruction due to left paraduodenal hernia with malrotation of midgut in a 55-year-old male patient

Direct and indirect arsenic release from soaps by unhygienic use in tubewells

Microorganisms have been implicated in the release of arsenic into drinking water involving bio-electrochemical reactions. Iron reducer has been shown to release captive arsenic from insoluble ferric oxyhydroxide- arsenic oxide adduct. Sulphate reducing bacteria (SRB) and Enterobacteriaceae may play a similar role by releasing hydrogen sulphide. The case of arsenic mobilization in water may be complex and varied. Arsenic contamination in Kanpur, northern India, 1000 km upstream of the Gangetic delta, added a new dimension to understanding the cause of its release in water. We propose that passive arsenic carried by the Ganges in the soil for centuries may be activated by unhygienic use of tubewells during the past three decades. We modelled the soil redox-chemistry prevalent under such conditions. We show that SRB grow in the vicinity of tubewells due to the availability of abundant food as fatty acids and sulphate as electron acceptors from soaps and detergents to release arsenic. In the absence of soap, Enterobacteriaceae play the same role. We also show that 26 commonly used soaps and detergents in India contain alarmingly high concentration of soluble arsenic, contaminating surface water

Concurrent parathyroid carcinoma and adenoma: A rare presentation of a rarer disease entity

Parathyroid carcinoma is a rare disease. But multiglandular parathyroid neoplasm is even rarer. A high level of suspicion, on the basis of clinical, hematological tests and intraoperative findings is necessary to treat this disease entity, particularly in the absence of palpable neck masses. Preoperative localization is important. Bilateral neck exploration should be done routinely and all 4 glands seen to avoid missing out other pathological glands

The Repeatability and Reproducibility Problem in the CVD Synthesis of 2D Materials: Towards a More Efficient and Sustainable Synthetic Process

Though Chemical Vapor Deposition (CVD) is a versatile process that has been widely used for synthesizing graphene, hexagonal boron nitride (h BN) and other 2-D materials, the process is plagued by issues of repeatability and reproducibility, the two important pillars of the scientific method. The primary reason for this is that we do not know or can directly measure the reaction environment inside the reactor (flow and thermal fields and reactant concentrations) that controls the growth process and the final film characteristics. In turn, we are unsure about the external parameters that control this reaction environment and can be measured instead. Consequently, experimental details currently monitored and reported in the literature are insufficient to ensure reproducibility, with process details typically reported only partially, and details about the reactor not included at all, further compounding the problem. In this paper, using the example of a hot-wall tube reactor that is typically used in the laboratory and the Computational Fluid Dynamics toolbox OpenFOAM, we have simulated the reactor environment and identified measurable reactor and process parameters that control this environment and explored its sensitivity to these external parameters. Based on our findings, we have devised a straightforward protocol for experimentalists to use for monitoring and reporting CVD processes in literature so that they become repeatable and reproducible, and, aid in analyzing and studying processes and mechanisms, rapid testing of ideas, process scale-up and an overall faster and more sustainable progress of the field

Repeatability and Reproducibility in the Chemical Vapor Deposition of 2D Films:A Physics-Driven Exploration of the Reactor Black Box

Although chemical vapor deposition (CVD) remains the method of choice for synthesizing defect-free and high-quality 2D films (such as graphene and h-BN), the method has serious issues with process repeatability and reproducibility. This makes it difficult to build up from the literature, test a hypothesis quickly, or scale up a process. The primary reason for this is that the CVD reactor, to this day, remains a black box with a reaction environment that is poorly understood and cannot be measured or monitored directly. Consequently, it is also difficult to study process kinetics and growth mechanisms and correlate experimental results to atomic-level simulations. A possible way to overcome this problem is to use Computational Fluid Dynamics (CFD), both to identify the measurable external (process and reactor) parameters that control the reaction environment and to simulate this reaction environment and understand how it changes when these controllable external parameters are varied. This paper describes how this may be done in practice using the growth of single-layer graphene in a hot-wall tube reactor as the representative case and the CFD toolbox OpenFOAM. Based on our findings, we have shown why it is critical (1) to understand the flow properties inside the reactor and combine it with experimental results to study the growth process for graphene and other 2D films and (2) to measure, monitor, and report all relevant external parameters to ensure process repeatability and reproducibility

Iridium and Ruthenium Catalyzed Syntheses, Hydroborations, and Metathesis Reactions of Alkenyl-Decaboranes

The selective syntheses of new classes of 6,9-dialkenyl- and 6-alkenyl-decaboranes and 6-alkyl-9-alkenyl-decaboranes have been achieved via iridium and ruthenium catalyzed decaborane and 6-alkyl-decaborane alkyne-hydroborations. Reactions employing [Cp*IrCl₂]₂ and [RuCl₂(<i>p</i>-cymene)]₂ precatalysts gave β-E-alkenyl-decaboranes, while the corresponding reactions with [RuI₂(<i>p</i>-cymene)]₂ gave the α-alkenyl-decaborane isomers, with the differences in product selectivity suggesting quite different mechanistic steps for the catalysts. The alkenyl-decaboranes were easily converted to other useful derivatives, including coupled-cage and functionally substituted compounds, via iridium-catalyzed hydroborations and ruthenium-catalyzed homo and cross olefin-metathesis reactions

Inside the CVD “Black Box”: A Physics-Driven Exploration of Reactor Conditions during Graphene Growth

Though more than a decade has passed since the first report of the chemical vapor deposition (CVD) of graphene on metal substrates, the CVD reactor resembles something of a black-box. The process flow conditions, and, temperature and reactant distribution profiles are poorly understood which causes significant repeatability and reproducibility issues. This also affects studies on the growth mechanism of graphene and the synthesis of completely defect free products. To address these challenges, the open source computational fluid dynamics toolbox OpenFOAM is used for the first systematic exploration of reactor conditions for the synthesis of single crystal and single layer graphene (SLG) in a tube reactor that is typically used in the laboratory. It is found that the reactor flow conditions are in the turbulent regime, and, the temperatures of the 50-100 μm thick copper foils on which graphene is grown are not uniform but have large temperature gradients with a sensitivity to the system pressure, the total mass flow rate and the process gas composition that increases with decreasing foil thickness. Furthermore, both the foil and gas temperatures can be manipulated by modifying the mass flow rates of Ar and H2 in the process gas mix. Based on this new-found knowledge, a process window was identified where the amount of Ar gas in the reactor was optimized to mimic cold-wall like conditions inside the hot-wall reactor and that favored the synthesis of pristine SLG films (while hotter reactor conditions produced films with numerous unwanted adlayers)