Reactions of Glutathione with Carcinogenic Esters of <i>N</i>-Arylhydroxamic Acids

The nitrenium ions 7a and 7b derived from hydrolysis of N-(sulfonatooxy)-N-acetyl-2-aminofluorene (1a) and N-(sulfonatooxy)-N-acetyl-4-aminobiphenyl (1b) are trapped by glutathione anion (GS-) with selectivity ratios, kgs−/ks, of 8200 ± 600 M-1 and 300 ± 15 M-1, respectively. Since ks is known for both of these ions under our reaction conditions, kgs− can be calculated. For 7a, kgs− is 6.3 × 108 M-1 s-1, and for 7b, kgs− is 1.8 × 109 M-1 s-1. Under physiological conditions (50−100 μM GS-) neither ion would be efficiently trapped by GS-. Some of the GSH adducts isolated in this study (4 from 1a, 11 and 12 from 1b) are not derived from nitrenium ion trapping. They arise from GS- trapping of the quinol imines 8a and 8b, which are the initial products of trapping of 7a and 7b by H2O. This reaction is very efficient at physiological GS- concentrations and could lead to significant GSH depletion in vivo. Although it has been known for some time that quinol imines such as 8a and 8b are major hydrolysis products of carcinogenic esters of N-arylhydroxylamines and N-arylhydroxamic acids, no physiological role has been previously suggested for these materials

sj-docx-1-aph-10.1177_10105395231204181 – Supplemental material for Association Between Temporary Employment and Gradient Health Outcomes Among Chinese Workers

Supplemental material, sj-docx-1-aph-10.1177_10105395231204181 for Association Between Temporary Employment and Gradient Health Outcomes Among Chinese Workers by Long Hao and Jing Lin in Asia Pacific Journal of Public Health</p

Reactions of Glutathione with Carcinogenic Esters of <i>N</i>-Arylhydroxamic Acids

The nitrenium ions 7a and 7b derived from hydrolysis of N-(sulfonatooxy)-N-acetyl-2-aminofluorene (1a) and N-(sulfonatooxy)-N-acetyl-4-aminobiphenyl (1b) are trapped by glutathione anion (GS-) with selectivity ratios, kgs−/ks, of 8200 ± 600 M-1 and 300 ± 15 M-1, respectively. Since ks is known for both of these ions under our reaction conditions, kgs− can be calculated. For 7a, kgs− is 6.3 × 108 M-1 s-1, and for 7b, kgs− is 1.8 × 109 M-1 s-1. Under physiological conditions (50−100 μM GS-) neither ion would be efficiently trapped by GS-. Some of the GSH adducts isolated in this study (4 from 1a, 11 and 12 from 1b) are not derived from nitrenium ion trapping. They arise from GS- trapping of the quinol imines 8a and 8b, which are the initial products of trapping of 7a and 7b by H2O. This reaction is very efficient at physiological GS- concentrations and could lead to significant GSH depletion in vivo. Although it has been known for some time that quinol imines such as 8a and 8b are major hydrolysis products of carcinogenic esters of N-arylhydroxylamines and N-arylhydroxamic acids, no physiological role has been previously suggested for these materials

Datasheet1_The impact of environmental disclosure and the quality of financial disclosure and IT adoption on firm performance: Does corporate governance ensure sustainability?.DOCX

Introduction: The study’s motivation is to investigate the role of environmental and financial disclosure, IT adoption, and good governance on firms’ sustainability from 1990–2019. A sample of 75 financial institutions enlisted in Bangladesh’s capital market was considered for relevant data collection.Methodology: Secondary data sources were used for data accumulation, including annual reports of target FIs, economic review reports, and central banks publication. Several econometrical techniques have been implemented to document the empirical nexus and the elasticities of explained variables on firm performance.Findings: In terms of baseline assessment, the study revealed a positive and statistically significant association between a firm’s sustainability and target explanatory variables. Furthermore, the study extended the empirical valuation by implementing a system-GMM and documented a positive linkage between financial and environmental disclosure, IT adaptation, good governance, and the firm’s performance sustainability.Discussion: These study findings suggest that information symmetry, investor protection, and access to financial services foster and stabilize the firms’ performance. Concerning corporate governance’s mediating effect, the study established a mediating role with positive influences on financial performance augmentation. On the policy ground, the study postulated that financial policymakers should address fairness and integrity in disclosing information to the public. Enforcement has to be initiated to ensure good governance.</p

Correlation of Azide/Solvent Selectivities for Nitrenium Ions with ab Initio Hydration Energies: Understanding the Kinetic Lability of Nitrenium Ions in Aqueous Solution

The experimentally determined azide/solvent selectivity data (log S) for 22 nitrenium ions (1a−v) were compared to the relative hydration energies (ΔE) calculated for these same ions at the RHF/6-31G*//3-21G level of theory. Except for the most reactive (least selective) of these ions (N-phenylnitrenium (1a), N-acetyl-N-phenylnitrenium (1b), and N-acetyl-N-(2-naphthyl)nitrenium (1d)), there is a good linear correlation of log S with ΔE that is broken only by the most selective ion for which the calculation was performed (N-(4‘-methoxy-4-biphenylyl)nitrenium (1r)). The deviation from linearity of the highly reactive ions is likely caused by the onset of preassociation trapping by N3- for ions with rate constants for solvent trapping, ks, of at least 1010 s-1. The preassociation process leads to approximately constant and low azide/solvent selectivities (log S ≈ 0.0) for these ions. Both the experimental log S values and the calculated ΔE values show that π-donor substituents in the para-position of the proximal ring of the ion have a remarkably strong stabilizing effect on the nitrenium ion that is not observed in carbenium ions of analogous structure, or in σ+ parameters. Substituents in the distal ring of a series of N-(4-biphenylyl)nitrenium ions were previously shown by Ren and McClelland to behave in a way expected for a benzylic carbenium ion, and our calculated ΔE values for these same ions also show a pattern that is carbenium ion-like. These results add to the growing experimental data that suggests that the dominant canonical form of most N-arylnitrenium ions is the iminocyclohexadienyl cation-like structure II. Calculated charge densities and LUMO coefficients for the nitrenium ions are of some use in rationalizing the regioselectivities of the reactions of small anionic nucleophiles and H2O with these ions, but this approach is not very useful in predicting the regioselectivities of softer carbon, nitrogen, or sulfur nucleophiles

Table_1_Effects of Paternal Obesity on Fetal Development and Pregnancy Complications: A Prospective Clinical Cohort Study.xlsx

ObjectivesTo evaluate the association between paternal obesity and fetal development and pregnancy complications.Study DesignThis prospective cohort clinical trial analyzed data from 7683 women with singleton pregnancies. All study subjects were sequentially divided into four groups based on paternal BMI. We compared the differences in fetal growth and pregnancy complications between different paternal BMI groups by univariate logistic regression and independent t-test. Finally, the independent predictors of SGA and macrosomia were determined.ResultsThe incidences of preeclampsia, cesarean section, SGA, macrosomia, and postpartum hemorrhage in the paternal obesity group were significantly higher than the normal BMI group. With the increase of paternal BMI, fetal ultrasound measurement parameter, neonatal and placental weight showed an increasing trend (trend P ConclusionPaternal obesity can affect fetal growth parameters and placental development, which has an adverse impact on pregnancy outcomes. Optimizing the paternal BMI will help improve the health of the next generation.</p

Does successful surgical correction of childhood large angle exotropia in adults make any difference to binocularity and quality of life?

Background/Aim: Strabismus surgery could achieve motor alignment and improve health-related quality of life (HRQOL) in adults with large angle exotropia, but whether it could improve binocularity and whether the binocularity is associated with HRQOL are unknown. The aim of this study is to evaluate the binocularity and HRQOL following successful surgical correction of childhood large angle exotropia in adults. Methods: Consecutive adults with childhood large angle exotropia (≥90 prism diopters) who underwent strabismus surgery in the Department of Ophthalmology and Vision Science, Eye and ENT Hospital, Shanghai Medical School, Fudan University were enrolled. Static and dynamic stereopsis tests were performed before surgery and 1 month after surgery. At the same time, Adult Strabismus-20 (AS-20), and Amblyopia and Strabismus questionnaire (A&SQ) were investigated. Results: A total of 29 adults achieved successful alignment: 18 intermittent exotropes (IXT) and 11 constant exotropes (CXT). One month after surgery, stereopsis was demonstrated better in all types of tests (p x2 = 7.62 p = .008). All HRQOL scores showed statistically significant improvement after surgery (p t = 2.24, p = .03) and the functional score (t = 2.92, p = .007) of AS-20, and the functional score (t = 3.06, p= .005) of A&SQ than CXT group. Only the change of the functional score of A&SQ was demonstrated a statistically significant correlation with the normal stereopsis (t = 2.67, p = .02). Conclusions: The stereopsis and HRQOL in adults with childhood large angle exotropia can be improved after successful surgical correction. More patients in IXT group gained normal stereopsis correlated with better functional aspects of HRQOL.</p

Improved FTA Methodology and Application to Subsea Pipeline Reliability Design

<div><p>An innovative logic tree, Failure Expansion Tree (FET), is proposed in this paper, which improves on traditional Fault Tree Analysis (FTA). It describes a different thinking approach for risk factor identification and reliability risk assessment. By providing a more comprehensive and objective methodology, the rather subjective nature of FTA node discovery is significantly reduced and the resulting mathematical calculations for quantitative analysis are greatly simplified. Applied to the Useful Life phase of a subsea pipeline engineering project, the approach provides a more structured analysis by constructing a tree following the laws of physics and geometry. Resulting improvements are summarized in comparison table form.</p></div

Rank Order Analysis of Useful Life factors.

<p>Calculations for ranking are based on the organization of the FET in Fig. 3. Under Source Reference Codes, values are from <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0093042#pone.0093042-Xie3" target="_blank">[23]</a>, <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0093042#pone.0093042.s003" target="_blank">Table S3</a>. Letters and “?” were not identified or evaluated by the original FTA, so corresponding probability data are unavailable. For demonstration purposes only, missing items are arbitrarily divided equally based on the number of nodes within a given level and“?” are denoted as “0”. Obviously, proper values should be inserted by field experts or suitably researched.</p

A typical Fault Tree analysis.

<p>This example for a Subsea Pipeline System is taken from <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0093042#pone.0093042-Xie1" target="_blank">[3]</a>.</p