16 research outputs found
Understanding the decomposition reaction mechanism of chrysanthemic acid: a computational study
<p>Abstract</p> <p>Background</p> <p>Chrysanthemic acid (<b>CHA</b>) is a major product from the photodecomposition of pyrethrin which is an important class of pesticide compounds.</p> <p>In the following paper, Hybrid density functional theory (DFT) calculations of the potential energy surface (PES) for three possible channels decomposition of chrysanthemic acid <b>(</b>cis-trans isomerization, rearrangement and fragmentation) have been carried at the B3LYP/6-311+G** level of theory. DFT was employed to optimize the geometry parameters of the reactants, transition states, intermediates and products based on detailed potential energy surfaces (PES).</p> <p>Results</p> <p>Our results suggest that all three pathways of <b>CHA </b>are endothermic. DFT calculations revealed that the activation barriers for cis-trans isomerization are low, leading to a thermodynamically favorable process than other two pathways. We also investigated the solvent effect on the PES using the polarizable continuum model (PCM). In addition, time-dependent density functional theory (TDDFT) calculations showed that these reactions occur in the ground state rather than in an excited state.</p> <p>Conclusion</p> <p>The rearrangement process seems to be more favorable than the decomposition of <b>CHA </b>to carbene formation. The solvent effect calculations indicated no changes in the shape of the PES with three continua (water, ethanol and cyclohexane), although the solvents tend to stabilize all of the species.</p
Evaluation of appendicitis risk prediction models in adults with suspected appendicitis
Background
Appendicitis is the most common general surgical emergency worldwide, but its diagnosis remains challenging. The aim of this study was to determine whether existing risk prediction models can reliably identify patients presenting to hospital in the UK with acute right iliac fossa (RIF) pain who are at low risk of appendicitis.
Methods
A systematic search was completed to identify all existing appendicitis risk prediction models. Models were validated using UK data from an international prospective cohort study that captured consecutive patients aged 16â45âyears presenting to hospital with acute RIF in March to June 2017. The main outcome was best achievable model specificity (proportion of patients who did not have appendicitis correctly classified as low risk) whilst maintaining a failure rate below 5 per cent (proportion of patients identified as low risk who actually had appendicitis).
Results
Some 5345 patients across 154 UK hospitals were identified, of which twoâthirds (3613 of 5345, 67·6 per cent) were women. Women were more than twice as likely to undergo surgery with removal of a histologically normal appendix (272 of 964, 28·2 per cent) than men (120 of 993, 12·1 per cent) (relative risk 2·33, 95 per cent c.i. 1·92 to 2·84; Pâ<â0·001). Of 15 validated risk prediction models, the Adult Appendicitis Score performed best (cutâoff score 8 or less, specificity 63·1 per cent, failure rate 3·7 per cent). The Appendicitis Inflammatory Response Score performed best for men (cutâoff score 2 or less, specificity 24·7 per cent, failure rate 2·4 per cent).
Conclusion
Women in the UK had a disproportionate risk of admission without surgical intervention and had high rates of normal appendicectomy. Risk prediction models to support shared decisionâmaking by identifying adults in the UK at low risk of appendicitis were identified
Gender-Specificity in Viewing Time Among Heterosexual Women
Measures of sexual interest tend to be more gender-specific in heterosexual men than in heterosexual women. Cognitive measures, such as viewing time to attractive stimuli, may also show similar patterns of gender-specificity or nonspecificity among men and women and thus serve as useful adjuncts to more direct measures of sexual interest. The objectives of the present research were to determine the extent of gender-specificity in women's viewing times for female pictures (varying in their perceived physical attractiveness) and explore the influence of social comparison of physical appearance on these patterns of responses. In Study 1, we recorded only women's viewing times for pictures of both genders, measured self-reported menstrual cycle phase, and manipulated the waist-to-hip ratio of the women in the female pictures. In Study 2, we recorded women's and men's viewing times, self-reported sexual attraction to pictures of males and females, and physical appearance social comparison. Study 1 found that heterosexual women's viewing time toward female pictures was not associated with manipulation of the perceived attractiveness of those pictures. Study 2 found that heterosexual men were more gender-specific than heterosexual women in their viewing time patterns. We also found that reported sexual attraction and physical appearance social comparison were associated with heterosexual women's viewing times for female pictures, while heterosexual men's viewing times were associated with sexual attraction only. Our results are discussed in relation to the utility of viewing time as an indicator of visual attention toward attractive or sexually appealing visual stimuli.</p