Ruthenium and osmium carbonyl clusters incorporating stannylene and stannyl ligands

The reaction of [Ru₃ (CO)₁₂] with Ph₃SnSPh in refluxing benzene furnished the bimetallic Ru-Sn compound [Ru₃(CO)₈(μ-SPh)₂(μ3-SnPh₂)(SnPh₃)₂] 1 which consists of a SnPh₂ stannylene bonded to three Ru atoms to give a planar tetra-metal core, with two peripheral SnPh₃ ligands. The stannylene ligand forms a very short bond to one Ru atom [Sn-Ru 2.538(1) Å] and very long bonds to the other two [Sn-Ru 3.074(1) Å]. The germanium compound [Ru₃(CO)₈(μ-SPh)₂(μ₃-GePh₂)(GePh₃)₂] 2 was obtained from the reaction of [Ru₃ (CO)₁₂] with Ph₃GeSPh and has a similar structure to that of 1 as evidenced by spectroscopic data. Treatment of [Os₃(CO)₁₀(MeCN)₂] with Ph₃SnSPh in refluxing benzene yielded the bimetallic Os-Sn compound [Os₃(CO)₉(μ-SPh)(μ₃-SnPh₂)(MeCN)(ƞ¹-C₆H₅)] 3. Cluster 3 has a superficially similar planar metal core, but with a different bonding mode with respect to that of 1. The Ph₂Sn group is bonded most closely to Os(2) and Os(3) [2.7862(3) and 2.7476(3) Å respectively] with a significantly longer bond to Os(1), 2.9981(3) Å indicating a weak back-donation to the Sn. The reaction of the bridging dppm compound [Ru₃(CO)₁₀(μ-dppm)] with Ph₃SnSPh afforded [Ru₃(CO)₆(μ-dppm)(μ₃-S)(μ₃-SPh)(SnPh₃)] 5. Compound 5 contains an open triangle of Ru atoms simultaneously capped by a sulfido and a PhS ligand on opposite sides of the cluster with a dppm ligand bridging one of the Ru-Ru edges and a Ph₃Sn group occupying an axial position on the Ru atom not bridged by the dppm ligand

An electron-deficient triosmium cluster containing the thianthrene ligand: Synthesis, structure and reactivity of [Os₃(CO)₉(μ3-η2-C₁₂H₇S₂)(μ-H)]

Reaction of [Os₃(CO)₁₀(CH₃CN)₂] with thianthrene at 80 °C leads to the nonacarbonyl dihydride compound [Os₃(CO)₉(μ-3,4-η²-C₁₂H₆S₂)(μ-H)₂] (1) and the 46-electron monohydride compound [Os₃(CO)₉(μ₃-η²-C₁₂H₇S₂)(μ-H)] (2). Compound 2 reacts reversibly with CO to give the CO adduct [Os₃(CO)₁₀(μ-η²-C₁₂H₇S₂)(μ-H)] (3) whereas with PPh₃ it gives the addition product [Os₃(CO)₉)(PPh₃)(μ-η²-C₁₂H₇S₂)(μ-H)] (4) as well as the substitution product 1,2-[Os₃(CO)₁₀ ((PPh₃)₂] (5) Compound 2 represents a unique example of an electron-deficient triosmium cluster in which the thianthrene ring is bound to cluster by coordination of the sulfur lone pair and a three-center-two-electron bond with the C(2) carbon which bridges the same edge of the triangle as the hydride. Electrochemical and DFT studies which elucidate the electronic properties of 2 are reported

Solubility of CO2 in Aqueous Solutions of 2-Amino-2-Methyl-1-Propanol at High Pressure

Carbon dioxide is one of the major green house gases. It is removed from different streams using amine absorption process. Sterically hindered amines are suggested as good CO2 absorbers. Solubility of carbon dioxide (CO2) was measured in aqueous solutions of 2-Amino-2-methyl-1-propanol (AMP) at temperatures 30 oC, 40 oC and 60 oC. The effect of pressure and temperature was studied over various concentrations of AMP. It has been found that pressure has positive effect on CO2 solubility where as solubility decreased with increasing temperature. Absorption performance of AMP increased with increasing pressure. Solubility of aqueous AMP was compared with mo-ethanolamine (MEA) and the absorption capacity of aqueous solutions of AMP was found to be better

Global age-sex-specific mortality, life expectancy, and population estimates in 204 countries and territories and 811 subnational locations, 1950–2021, and the impact of the COVID-19 pandemic: a comprehensive demographic analysis for the Global Burden of Disease Study 2021

Background Estimates of demographic metrics are crucial to assess levels and trends of population health outcomes. The profound impact of the COVID-19 pandemic on populations worldwide has underscored the need for timely estimates to understand this unprecedented event within the context of long-term population health trends. The Global Burden of Diseases, Injuries, and Risk Factors Study (GBD) 2021 provides new demographic estimates for 204 countries and territories and 811 additional subnational locations from 1950 to 2021, with a particular emphasis on changes in mortality and life expectancy that occurred during the 2020–21 COVID-19 pandemic period. Methods 22 223 data sources from vital registration, sample registration, surveys, censuses, and other sources were used to estimate mortality, with a subset of these sources used exclusively to estimate excess mortality due to the COVID-19 pandemic. 2026 data sources were used for population estimation. Additional sources were used to estimate migration; the effects of the HIV epidemic; and demographic discontinuities due to conflicts, famines, natural disasters, and pandemics, which are used as inputs for estimating mortality and population. Spatiotemporal Gaussian process regression (ST-GPR) was used to generate under-5 mortality rates, which synthesised 30 763 location-years of vital registration and sample registration data, 1365 surveys and censuses, and 80 other sources. ST-GPR was also used to estimate adult mortality (between ages 15 and 59 years) based on information from 31 642 location-years of vital registration and sample registration data, 355 surveys and censuses, and 24 other sources. Estimates of child and adult mortality rates were then used to generate life tables with a relational model life table system. For countries with large HIV epidemics, life tables were adjusted using independent estimates of HIV-specific mortality generated via an epidemiological analysis of HIV prevalence surveys, antenatal clinic serosurveillance, and other data sources. Excess mortality due to the COVID-19 pandemic in 2020 and 2021 was determined by subtracting observed all-cause mortality (adjusted for late registration and mortality anomalies) from the mortality expected in the absence of the pandemic. Expected mortality was calculated based on historical trends using an ensemble of models. In location-years where all-cause mortality data were unavailable, we estimated excess mortality rates using a regression model with covariates pertaining to the pandemic. Population size was computed using a Bayesian hierarchical cohort component model. Life expectancy was calculated using age-specific mortality rates and standard demographic methods. Uncertainty intervals (UIs) were calculated for every metric using the 25th and 975th ordered values from a 1000-draw posterior distribution. Findings Global all-cause mortality followed two distinct patterns over the study period: age-standardised mortality rates declined between 1950 and 2019 (a 62·8% [95% UI 60·5–65·1] decline), and increased during the COVID-19 pandemic period (2020–21; 5·1% [0·9–9·6] increase). In contrast with the overall reverse in mortality trends during the pandemic period, child mortality continued to decline, with 4·66 million (3·98–5·50) global deaths in children younger than 5 years in 2021 compared with 5·21 million (4·50–6·01) in 2019. An estimated 131 million (126–137) people died globally from all causes in 2020 and 2021 combined, of which 15·9 million (14·7–17·2) were due to the COVID-19 pandemic (measured by excess mortality, which includes deaths directly due to SARS-CoV-2 infection and those indirectly due to other social, economic, or behavioural changes associated with the pandemic). Excess mortality rates exceeded 150 deaths per 100 000 population during at least one year of the pandemic in 80 countries and territories, whereas 20 nations had a negative excess mortality rate in 2020 or 2021, indicating that all-cause mortality in these countries was lower during the pandemic than expected based on historical trends. Between 1950 and 2021, global life expectancy at birth increased by 22·7 years (20·8–24·8), from 49·0 years (46·7–51·3) to 71·7 years (70·9–72·5). Global life expectancy at birth declined by 1·6 years (1·0–2·2) between 2019 and 2021, reversing historical trends. An increase in life expectancy was only observed in 32 (15·7%) of 204 countries and territories between 2019 and 2021. The global population reached 7·89 billion (7·67–8·13) people in 2021, by which time 56 of 204 countries and territories had peaked and subsequently populations have declined. The largest proportion of population growth between 2020 and 2021 was in sub-Saharan Africa (39·5% [28·4–52·7]) and south Asia (26·3% [9·0–44·7]). From 2000 to 2021, the ratio of the population aged 65 years and older to the population aged younger than 15 years increased in 188 (92·2%) of 204 nations. Interpretation Global adult mortality rates markedly increased during the COVID-19 pandemic in 2020 and 2021, reversing past decreasing trends, while child mortality rates continued to decline, albeit more slowly than in earlier years. Although COVID-19 had a substantial impact on many demographic indicators during the first 2 years of the pandemic, overall global health progress over the 72 years evaluated has been profound, with considerable improvements in mortality and life expectancy. Additionally, we observed a deceleration of global population growth since 2017, despite steady or increasing growth in lower-income countries, combined with a continued global shift of population age structures towards older ages. These demographic changes will likely present future challenges to health systems, economies, and societies. The comprehensive demographic estimates reported here will enable researchers, policy makers, health practitioners, and other key stakeholders to better understand and address the profound changes that have occurred in the global health landscape following the first 2 years of the COVID-19 pandemic, and longer-term trends beyond the pandemic

σ-Bonded organometallics of molybdenum, iron and cobalt derived from 1,8-bis(bromomethyll- naphthalene

906-908The monoanionic metal carbonylate, Na [MO(η5-C5H5)(CO)3]reacts with 1,8- is(bromomethyl)naphthalene in refluxing THF to give the σ-bonded [C10H6(CH2)2{Mo- (η5- C5H5)(CO)3}2] (I), whereas Na[Fe(η5-C5H5)(CO)2] and Na[CO(CO)4] react with the ligand at room temperature to afford the σ-bonded [C10H6(CH2)2{Fe(η5-C5H5)(CO)2}2](II) and [C10H6(CH2)2{Co(CO)4}2](III), respectively. The complexes have been characterized by IR, PMR and mass spectra

New ruthenium carbonyl clusters containing unusual 5-sulfido-, 4-benzyne-, and thianthrene-derived ligands: Insertion of ruthenium into the thianthrene ring by C-S activation

Treatment of [Ru3(CO)12] with thianthrene in refluxing toluene afforded [( 4-S)Ru4( -CO)2(CO)9( 4- 2-C6H4)] (1), [( 5-S)Ru6( -CO)2(CO)15( - 3-C12H8S)] (2), and [( 5-S)Ru5( -CO)2(CO)11( - 3-C12H8S)( 4- 2-C6H4)] (3) in 18%, 8%, and 16% yields, respectively. Thermolysis of 2 in refluxing heptane gave compounds 1 and 3. A similar thermolysis of 3 in refluxing toluene gave 1 in 90% yield. Treatment of 3 with neat MeCN afforded the labile compound [( 5-S)Ru5( -CO)2(CO)10( - 3-C12H8S)( 4- 2-C6H4)(MeCN)] (4) in 73% yield. The reaction of 4 with P(OMe)3 gave the substitution product [( 5-S)Ru5( -CO)2(CO)10( - 3-C12H8S)( 4- 2-C6H4){P(OMe)3}] (5) in 52% yield. Compounds 1-4 have been structurally characterized. Compound 1 contains a 4-capping sulfido and a 4- 2-benzyne ligand, whereas 3, 4, and 5 contain 5-sulfido and 4- 2-benzyne ligands. The latter three compounds provide rare examples of 5-sulfido and metal-assisted opening of the thianthrene ligand on polynuclear centers. In compounds 1, 3, and 4 the 4- 2-benzyne ligand is perpendicular to the Ru4 face of the clusters and represents a previously uncharacterized bonding mode for benzyne

Using SPOT-7 for Nitrogen Fertilizer Management in Oil Palm

Environmental concerns are growing about excessive applying nitrogen (N) fertilizers, especially in oil palm. Some conventional methods which are used to assess the amount of nutrient in oil palm are time-consuming, expensive, and involve frond destruction. Remote sensing as a non-destructive, affordable, and efficient method is widely used to detect the concentration of chlorophyll (Chl) from canopy plants using several vegetation indices (VIs) because there is an influential relation between the concentration of N in the leaves and canopy Chl content. The objectives of this research are to (i) evaluate and compare the performance of various vegetation indices (VIs) for measuring N status in oil palm canopy using SPOT-7 imagery (AIRBUS Defence & Space, Ottobrunn, Germany) to (ii) develop a regression formula that can predict the N content using satellite data to (iii) assess the regression formula performance on testing datasets by testing the coefficient of determination between the predicted and measured N contents. SPOT-7 was acquired in a 6-ha oil palm planted area in Pahang, Malaysia. To predict N content, 28 VIs based on the spectral range of SPOT-7 satellite images were evaluated. Several regression models were applied to determine the highest coefficient of determination between VIs and actual N content from leaf sampling. The modified soil-adjusted vegetation index (MSAVI) generated the highest coefficient of determination (R2 = 0.93). MTVI1 and triangular VI had the highest second and third coefficient of determination with N content (R2 = 0.926 and 0.923, respectively). The classification accuracy assessment of the developed model was evaluated using several statistical parameters such as the independent t-test, and p-value. The accuracy assessment of the developed model was more than 77%

Reduction in Door-to-Needle Time after Transfer of Thrombolysis Site from CCU to Emergency Department

Objective. Early restoration of coronary perfusion by thrombolysis or percutaneous coronary intervention is the main modality of treatment to salvage the ischemic myocardium. The earlier the procedure is completed, the greater the benefit is in saving myocardium and restoring its functions. The aim of the study is to compare the door-to-needle time (DNT) in acute ST elevation myocardial infarction (STEMI) in the period prior to December 2008 when the site of thrombolysis was in coronary care unit (CCU) and the period after that when the site was shifted to emergency department (ED). Methods. A retrospective, descriptive study was conducted at Al Khor Hospital, Qatar, in patients with acute STEMI who underwent thrombolysis at CCU and ED from April 2005 until December 2011, to compare the DNT, duration of hospitalization, and mortality. Results. A total of 211 patients with acute STEMI were eligible for thrombolysis; 58 patients were thrombolysed in the CCU and 153 in ED. The median DNT was reduced from 33.5 minutes in the CCU to 17 minutes in the ED representing a reduction of more than 50% with a P value of < 0.0001. Conclusion. The transfer of the thrombolysis site from CCU to the ED was associated with a dramatic and significant reduction in median door-to-needle time by more than half