Racial Inequities in the Control of Hypertension and the Explanatory Role of Residential Segregation: a Decomposition Analysis in the Brazilian Longitudinal Study of Adult Health (ELSA-Brasil).

The mechanisms underlying racial inequities in uncontrolled hypertension have been limited to individual factors. We investigated racial inequities in uncontrolled hypertension and the explanatory role of economic segregation in the Brazilian Longitudinal Study of Adult Health (ELSA-Brasil). All 3897 baseline participants with hypertension (2008-2010) were included. Uncontrolled hypertension (SBP ≥ 140 mmHg or DBP ≥ 90 mmHg), self-reported race (White/Brown/Black people), and neighborhood economic segregation (low/medium/high) were analyzed cross-sectionally. We used decomposition analysis, which describes how much a disparity would change (disparity reduction; explained portion) and remain (disparity residual; unexplained portion) upon removing racial differences in economic segregation (i.e., if Black people had the distribution of segregation of White people, how much we would expect uncontrolled hypertension to decrease among Black people). Age- and gender-adjusted prevalence of uncontrolled hypertension (39.0%, 52.6%, and 54.2% for White, Brown, and Black participants, respectively) remained higher for Black and Brown vs White participants, regardless of economic segregation. Uncontrolled hypertension showed a dose-response pattern with increasing segregation levels for White but not for Black and Brown participants. After adjusting for age, gender, education, and study center, unexplained portion (disparity residual) of race on uncontrolled hypertension was 18.2% (95% CI 13.4%; 22.9%) for Black vs White participants and 12.6% (8.2%; 17.1%) for Brown vs White participants. However, explained portion (disparity reduction) through economic segregation was - 2.1% (- 5.1%; 1.3%) for Black vs White and 0.5% (- 1.7%; 2.8%) for Brown vs White participants. Although uncontrolled hypertension was greater for Black and Brown vs White people, racial inequities in uncontrolled hypertension were not explained by economic segregation.

Determinants of Hispanic and non-Hispanic Workers' Intent to Work Past Age 65: An Analysis From the Life Course Perspective.

Background: The average retirement age in the United States (U.S.) has increased over the past few decades. However, the rate of increase for Hispanics is lower than that for non-Hispanics. For Hispanics, the decision to retire later may be more influenced by their migration history and context rather than health or finances. Objective: This study aims to explore the differences in the determinants of intentions to delay retirement (i.e., work beyond the age of 65) between Hispanics and non-Hispanic Whites in the U.S. Methods: A pooled sample was generated from all waves of the Health and Retirement Study (1992-2014), including a unique record for each non-institutionalized individual aged 55-61 who was employed. All eligible Hispanics (n = 3,663) were included, while a random sample of non-Hispanic Whites (n = 3,663) was selected. Logistic mixed models were conducted for each group, and a Two-fold Oaxaca-Blinder decomposition analysis was used to explore differences between the groups. Results: The results indicate that non-Hispanic Whites are more likely to plan to postpone retirement. Furthermore, significant differences were found between Hispanics and non-Hispanic Whites regarding their intentions to delay retirement, specifically related to socioeconomic indicators such as individual earnings, amount of debt, level of education, and parents' level of education. The differences between the groups were primarily influenced by the amount of debt, having a defined benefit plan, and parents' level of education, reflecting the cumulative disadvantage experienced by Hispanics over their life course. Conclusion: Most existing research on the topic has focused on middle-class Whites, while few studies have examined race or ethnicity as the primary focus or explored the extent to which commonly identified predictors of delayed retirement apply to different ethno-racial groups. This is significant because Hispanics and other disadvantaged groups tend to experience financial insecurity during retirement, which directly impacts their health and well-being.

Key drivers of the textile and clothing industry decarbonisation within the EU-27.

The European Union has identified the Textile and Clothing industry as one of the essential objectives towards carbon neutrality in 2050 in line with the "European Green Deal". There are no previous research papers focused on analysing the drivers and inhibitors of the past greenhouse gas emission changes of the textile and clothing industry in Europe. This paper aims to analyse the determinants of the changes in these emissions, and the disassociation level between emissions and economic growth, throughout the 27 Member States of the European Union, from 2008 to 2018. A Logarithmic Mean Divisia Index that explains the key drivers of the changes in greenhouse gas emissions of European Union Textile and Cloth industry and a Decoupling Index have been applied. The results generally conclude that the intensity and carbonisation effects are key factors that contribute to reducing greenhouse gas emissions. The lower relative weight of the textile and clothing industry throughout the EU-27 was noteworthy, and favours lower emissions, partially counteracted by the activity effect. Also, most Member States have been decoupling the industry's emissions from economic growth. Our policy recommendation shows that if further reductions in greenhouse gas emissions are to be achieved, energy efficiency improvements and cleaner use of energy sources would offset the potential increase in emissions of this industry as a result of a relative increase in its gross value added.

Performance of a pharmaceutical services regionalization strategy policy in Minas Gerais, Brazil: Pre-post analysis from ERAF project.

Background: In 2016, the Brazilian state of Minas Gerais (∼20 million people), implemented the ERAF policy ("Regionalization Strategy of Pharmaceutical Services") in an effort to improve medicine procurement and distribution within primary care. We evaluated the impact of the policy on three main goals: price reductions, volume increases, and expansion of therapeutic options. Methods: We analyzed the procurement data from the Integrated System of Management of Pharmaceutical Services database in 2012 and 2018. We estimated the volume, drug mix, and expenditure indicators for all major therapeutic classes, and, in detail, for cardiovascular and nervous system drugs. We evaluated the expenditure drivers using decomposition analyses. Results: Overall, the expenditure increased by 14.5%, drug mix almost doubled, while the volume decreased by a third. Cardiovascular and neurological system drugs followed similar patterns. Decomposition analyses showed that prices and drug mix had positive effects while the volume had negative effects, resulting in an overall increase in expenditure. Conclusion: Our findings suggest that the ERAF policy cannot be considered effective as it has not fulfilled its intended purposes so far. Strategies to address the identified problems and to build a platform for a more sustainable long-lasting policy should be put in place by the government.

Health in Conflict Zones: Analyzing Inequalities in Mental Health in Colombian Conflict-Affected Territories.

Objectives: Colombia's civil conflict and persistent socio-economic disparities have contributed to mental health inequalities in conflict-affected territories. We explore the magnitude of mental health inequalities, contributing socio-economic factors, and sociodemographic characteristics that explain these differences. Methods: The study draws on data collected in 2018, using the household survey Conflicto, Paz y Salud (CONPAS) applied to 1,309 households in Meta, Colombia. Logistic regression and decomposition analysis were used to analyze the risk of mental health disorders, measured with the Self-Reporting Questionnaire -20 (SRQ-20). Results: Individuals with lower socio-economic status are at a higher risk for mental health disorders. Forced displacement accounts for 31% of the measured mental health inequalities. Disparities in employment, education level, disability and conflict incidence between municipalities are other contributing factors. Women and people with disabilities are respectively 2.3 and 1.2 times more prone to present a mental health disorder. Conclusion: It is necessary to tackle the identified risk factors and sociodemographic circumstances that contribute to mental health inequalities in conflict-affected territories, as these hinder adequate/equitable access to mental health services.

Brazilian Environmental-Economic Accounting for Water: A structural decomposition analysis.

The UN Sustainable Development Goals constitute a bench of directives with a universal scope to establish actions to mitigate poverty and protect the environment. Benefiting from the Environmental-Economic Accounting for Water recently published in Brazil, it is possible to harmonize the demand of water and the economic sectors. To this end, this study conducted an input-output analysis and structural decomposition analysis to explore the water consumption of the Brazilian Economy and its driving forces during an unprecedented drought and economic recession between 2013 and 2015. The results indicate that the total variation of the water consumption in the period is 15%. Between 2013 and 2014, the total effect was positive, causing an increase of 45% in the embodied water consumption, having as main driver the final demand and the intensity effect. In the second period, the total intensity effect was negative, provoking a decrease of -10% in the total water consumption. The "Agriculture, livestock, forestry and fishing" is the main sector responsible for these positive and negative results, while the "Energy and gas natural supply" sector has a strategic position to avoid a structural increase on the economic water demand.

Underpinnings of entangled ethnical and gender inequalities in obesity in Cochabamba-Bolivia: an intersectional approach.

BACKGROUND: Social inequalities in obesity have been observed not only by gender but also between ethnic groups. Evidence on combined dimensions of inequality in health, and specifically including indigenous populations, is however scarce, and presents a particularly daunting challenge for successful prevention and control of obesity in Bolivia, as well as worldwide. OBJECTIVE: The aims of this study were i) to examine intersectional inequalities in obesity and ii) to identify the factors underlying the observed intersectional inequalities. METHODS: An intersectional approach study was employed, using the information collected in a cross-sectional community-based survey. The sample consisted of youth and adults with permanent residence in Cochabamba department (N = 5758), selected through a multistage sampling technique. An adapted version of the WHO-STEPS survey was used to collect information about Abdominal obesity and risk factors associated. Four intersectional positions were constructed from gender (woman vs. men) and ethnic group (indigenous vs. mestizo). Joint and excess intersectional disparities in obesity were estimated as absolute prevalence differences between binary groups, using binomial regression models. The Oaxaca-Blinder decomposition was applied to estimate the contributions of explanatory factors underlying the observed intersectional disparities, using Oaxaca command in Stata software v15.1. RESULTS: The prevalence of abdominal obesity had a higher prevalence in mestizos (men 35.01% and women 30.71%) as compared to indigenous (men 25.38% and women 27.75%). The joint disparity was estimated at 7.26 percentage points higher prevalence in the doubly advantaged mestizo men than in the doubly disadvantaged indigenous women. The gender referent disparity showed that mestizo-women had a higher prevalence than indigenous-women. The ethnic referent disparity showed that mestizo-men had a higher prevalence than indigenous men. The behavioural risk factors were the most important to explain the observed inequalities, while differences in socioeconomic and demographic factors played a less important role. CONCLUSION: Our study illustrates that abdominal obesity is not distributed according to expected patterns of structural disadvantage in the intersectional space of ethnicity and gender in Bolivia. In the Cochabamba case, a high social advantage was related to higher rates of abdominal obesity, as well as the behavioural risk factors associated with them.

Structure and bonding in triorganotin chlorides: a perspective from energy decomposition analysis.

The Sn-Cl chemical bond of four organotin halides (Me3SnCl, Et3SnCl, Bu3SnCl, and Ph3SnCl) was studied by using relativistic density functional theory in combination with a quantitative energy decomposition analysis to explain the formation of charged species. The σ orbital is the dominant contributor to the stabilization of the Sn-Cl bond, and the π-orbital interactions also have a significant contribution to the stabilization of Ph3Sn+ cation when the aromatic groups are bonded to the tin atom. The aromaticity of the phenyl groups delocalizes the positive charge, donating electrons to tin atom by conjugation. Although Me3SnCl and Ph3SnCl are constituted by groups which the size of the substituents is different, the interaction energies obtained with the energy decomposition analysis present similar values, which also occur with the thermodynamic parameters. Graphical abstract Organotin compounds have widely studied as a potential antitumoral agent. The mechanism in triorganotin compounds includes the formation of cation species, R3Sn+. This article studies the influence of the R groups on the rupture of Sn-Cl bond using the fragment analysis and quantitative energy decomposition analysis.

The impact of violence on Venezuelan life expectancy and lifespan inequality.

BACKGROUND: Venezuela is one of the most violent countries in the world. According to the United Nations, homicide rates in the country increased from 32.9 to 61.9 per 100 000 people between 2000 and 2014. This upsurge coincided with a slowdown in life expectancy improvements. We estimate mortality trends and quantify the impact of violence-related deaths and other causes of death on life expectancy and lifespan inequality in Venezuela. METHODS: Life tables were computed with corrected age-specific mortality rates from 1996 to 2013. From these, changes in life expectancy and lifespan inequality were decomposed by age and cause of death using a continuous-change model. Lifespan inequality, or variation in age at death, is measured by the standard deviation of the age-at-death distribution. RESULTS: From 1996 to 2013 in Venezuela, female life expectancy rose 3.57 [95% confidence interval (CI): 3.08-4.09] years [from 75.79 (75.98-76.10) to 79.36 (78.97-79.68)], and lifespan inequality fell 1.03 (-2.96 to 1.26) years [from 18.44 (18.01-19.00) to 17.41 (17.30-18.27)]. Male life expectancy increased 1.64 (1.09-2.25) years [from 69.36 (68.89-59.70) to 71.00 (70.53-71.39)], but lifespan inequality increased 0.95 (-0.80 to 2.89) years [from 20.70 (20.24-21.08) to 21.65 (21.34-22.12)]. If violence-related death rates had not risen over this period, male life expectancy would have increased an additional 1.55 years, and lifespan inequality would have declined slightly (-0.31 years). CONCLUSIONS: As increases in violence-related deaths among young men (ages 15-39) have slowed gains in male life expectancy and increased lifespan inequality, Venezuelan males face more uncertainty about their age at death. There is an urgent need for more accurate mortality estimates in Venezuela.

The Antagonist Effect of Nitrogen Lone Pair: 3 JHF versus 5 JHF.

The long-range scalar coupling constant between proton and fluorine nuclei, 5 JHF , is observed to be larger than 3 JHF in the pyrimidinyl moiety of voriconazole. A set of smaller molecules is chosen (fluorobenzene, N-methyl-2-fluoropyridine, N-methyl-3-fluoropyridine, 3-fluoropyridine, 5-pyrimidine, and 2-fluoropyridine) to evaluate the influence of the nitrogen atom in the experimental JHF values. Spectral aliased pure shift heteronuclear single quantum coherence spectroscopy (SAPS-HSQC) is applied to determine the relative sign between the JCF and JHF scalar couplings. Theoretical calculations show that the 3 JHF and 5 JHF coupling constants can be described mainly by a Fermi contact (FC) transmission mechanism. A decomposition analysis of JHF in terms of localized molecular orbital (LMO) contributions allows us to determine that the interaction involving the nitrogen lone pair (LPN) is the main reason for the larger 5 JHF compared to 3 JHF . Our analysis indicates that delocalization of LPN has a positive contribution to the long-range coupling, while a negative one is observed for 3 JHF .

A DFT study of the interaction between [Cd(H2O)3]2+ and monodentate O-, N-, and S-donor ligands: bond interaction analysis.

A series of B3LYP/6-311+G(d,p) calculations of the affinity of monodentate ligands for [Cd(H2O)3]2+ are performed. Three types of ligands containing O (phosphine oxide, lactam, amide, carboxylic acid, ester, ketone, aldehyde, ether, halohydrin, enol, furan), N (thiocyanate, amine, ammonia, azide), and S (thioester, thioketone, thiol, thiophene, disulfide) interacting atoms are investigated. The results show that phosphine oxide has the largest affinity for the cadmium cation due to the polarization of the P=O bond. As the P atom has a large atomic radius, the O atom can polarize the electronic cloud enhancing its amount of electronic charge and favoring the interaction with Cd2+. The affinity order found is phosphine oxide > thioester > lactam > amide > carboxylic acid > ester > thioketone > ketone > thiocyanate > amine > ammonia > aldehyde > ether > thiol > thiophene > enol > halohydrin > disulfide > azide > furan ligands. These results were also corroborated by the functional M06-2X. The electronic effects (resonance and induction) of neighboring groups of the interacting atom modulate the strength of metal-ligand binding. For almost all the O-donor ligands the electrostatic component has the same magnitude as the covalent term, while for the N- and S-donor ligands the covalent term is predominant. The polarization term accounts for twice the exchange term as part of the covalent component. The dispersion term varies less than 2 kcal mol-1 for the complexes analyzed. The Pauli repulsion term is correlated with the metal ligand distance, increasing in the compounds with decreased metal-ligand bond length. The charge between the interacting atoms is also strongly correlated with both the interacting strength and the electrostatic interaction component. The natural bond orbital analysis highlights correlations of the bond order, and S and P contributions of the interacting metal-ligand orbital with the coordination strength. Graphical abstract The affinity of 20 monodentate ligands with different functional groups for the [Cd(H2O)3]2+ cation is calculated based on the interaction enthalpy and Gibbs free energy for the substitution of one water molecule from the fully hydrated cation. The affinity is correlated with geometric, electronic, and energetic parameters of the ligands and the complexes as well as with energy decomposition and natural bond order analyses results.

A DFT study of hydrogen and methane activation by B(C6F5)3/P(t-Bu)3 and Al(C6F5)3/P(t-Bu)3 frustrated Lewis pairs.

This contribution presents a computational study aimed at understanding factors affecting barriers associated with the activation of the H-H bond in molecular hydrogen and the H-CH3 bond in methane mediated by intermolecular Frustrated Lewis Pairs (FLPs). The classical phosphine P(t-Bu)3 Lewis base in conjunction with two Lewis acids, B(C6F5)3 and Al(C6F5)3, were used as representative models of intermolecular FLPs. DFT calculations were performed using the dispersion corrected ωB97x-D functional, including toluene as a solvent through the PCM-SMD implicit solvent scheme. The results show that, in all cases, the activation barrier is larger for methane than for hydrogen. We conclude that the observed increase in the barrier for methane activation is due primarily to a larger distortion in methane compared to hydrogen to reach the transition state. Second, a large distortion of the Lewis acid to attain a better interaction with the σ-bond in methane was observed. Finally, we found that, for both hydrogen and methane activation, a considerable reduction in the free energy activation barrier is observed when the Lewis acid Al(C6F5)3 is used. From the results extracted in this study, we propose the use of alanes acids as good candidates for methane activation.

A density functional theory investigation of the interaction of the tetraaqua calcium cation with bidentate carbonyl ligands.

Calcium complexes with bidentate carbonyl ligands are important in biological systems, medicine and industry, where the concentration of Ca2+ is controlled using chelating ligands. The exchange of two water molecules of [Ca(H2O)6]2+ for one bidentate monosubstituted and homo disubstituted dicarbonyl ligand was investigated using the B3LYP/6-311++G(d,p) method. The ligand substituents NH2, OCH3, OH, CH3, H, F, Cl, CN and NO2 are functional groups with distinct electron-donating and -withdrawing effects that bond directly to the sp2 C atom of the carbonyl group. The geometry, charge and energy characteristics of the complexes were analyzed to help understand the effects of substituents, spacer length and chelation. Coordination strength was quantified in terms of the enthalpy and free energy of the exchange reaction. The most negative enthalpies were calculated for the coordination of bidentate ligands containing three to five methylene group spacers between carbonyls. The chelate effect contribution was analyzed based on the thermochemistry. The electronic character of the substituent modulates the strength of binding to the metal cation, as ligands containing electron-donor substituents coordinate stronger than those with electron-acceptor substituents. This is reflected in the geometric (bond length and chelating angle), electronic (atomic charges) and energetic (components of the total interacting energy) characteristics of the complexes. Energy decomposition analysis (EDA)-an approach for partitioning of the energy into its chemical origins-shows that the electrostatic component of the coordination is predominant, and yields relevant contribution of the covalent term, especially for the electron-withdrawing substituted ligands. The chelate effect of the bidentate ligands was noticeable when compared with substitution by two monodentate ligands. Graphical abstract The affinity of 18 bidentate carbonyl ligands toward the [Ca(H2O)4]2+ cation is evaluated in terms of energetic, geometric and electronic parameters of the isolated ligands and the substituted aqua complexes. The electronic effects-inductive and mesomeric-intrinsic to the molecular structure of each ligand are found to modulate the strength of the metal-ligand interaction. The effects of polysubstitution, chelation and the length of the alkyl spacers between the anchor points of the ligand are also analyzed.

Reactivity and regioselectivity in reactions of methyl and ethyl azides with cyclooctynes: activation strain model and energy decomposition analysis.

The structures and energies for the Huisgen 1,3-dipolar cycloaddition reactions of methyl and ethyl azides with some cyclooctynes and dibenzocyclooctynes were computed at the B3LYP/6-311++G(d,p) level. The activation strain model (ASM) and quantitative molecular orbital (MO) theory were used to investigate the reactivity and regiochemistry in these reactions. The energy decomposition analysis (EDA) was used to identify the intrinsic electronic factor that lead to the preferential formation of 1,7-regiochemistry products. The reactivity order agrees with formation of more synchronous transition states and lower distortion energies. For the reaction of N3Met with azacyclooctyne, the 1,7-regiochemistry preference is attributed to a lower FMO gap and a higher contribution of the polarization term of the interaction energy than for the 1,8-transition state. For the reaction with aza-dibenzocyclooctyne, the 1,7-preference is due to a lower strain energy and a more pronounced contribution of the exchange term of the interaction energy. Graphical Abstract In the reactions between methyl and ethyl azides with azacyclooctynes the regiochemistry is governed by the intrinsic electronic factors.