RESUMO
Phosphinooxazoline (PHOX) ligands have been used to control the regio- and enantioselectivity in a wide variety of metal-catalyzed reactions. Despite their widespread use, PHOX ligands have never been studied in metal-aryne complexes. Herein we report the first example of a PHOX-Ni aryne complex. As demonstrated in other systems, the differentiated P versus N donors and different steric environments of the unsymmetric ligand are able to induce regiocontrol. A 81:19 mixture of o-methoxy substituted aryne complexes is observed. Single-crystal X-ray crystallographic analysis, UV/vis spectroscopy, and cyclic voltammetry are used to gain further insight into the molecular and electronic structure of these complexes. Lastly, a methylation/deuteration sequence shows retention of the PHOX ligand-induced regiocontrol in the difunctionalized products and that the regiospecificity of these difunctionalizations is due to the trans influence of the P donor.
RESUMO
BACKGROUND: There is evidence that changes to the midface and lower third of the face in isolation contribute significantly to one's perception of the overall facial age. Since the spread of the coronavirus disease 2019 (COVID-19), mask wearing has become commonplace. To date, there have been no studies that explore how covering the lower third of the face impacts the perception of age. OBJECTIVES: The authors hypothesized that covering the lower third of the face with a mask will make a person appear younger. METHODS: One hundred consecutive plastic surgery patients were photographed in a standardized fashion, both masked and unmasked. A questionnaire for factors known to contribute to facial aging was administered. These photographs were randomized to 6 judges who estimated the patients' age and also quantified facial rhytids with the validated Lemperle wrinkle assessment score of 6. Data were analyzed using PROC MIXED analysis. RESULTS: Masked patients on average appeared 6.17% younger (mean difference = 3.16 years, P < 0.0001). Wrinkle assessment scores were 9.81% lower in the masked group (mean difference = 0.21, P = 0.0003). All subgroups appeared younger in a mask except for patients aged 18 to 40 years chronological age (P = 0.0617) and patients BMI > 35 (P = 0.5084). CONCLUSIONS: The mask group appeared younger and had lower overall and visible wrinkle assessment scores when compared with the unmasked group. This has implications for our understanding of the contributions of the lower third of the face to overall perceived facial age.
RESUMO
It has been argued that observers perceive actors' affordances via embodied simulation, that is, first perceiving their own affordance, which serves as a model for the actor's affordance, and then adjusting that model to account for differences between themselves and the actor. If so, then preventing observers from picking up information about their own affordances should cause several effects. Specifically, observers should make more errors about the actor's affordance compared to when the observer is free to pick up information about their own affordance. In addition, judgments about the actor's affordance should align better with the observer's affordance than with the actor's affordance, and increase in error as differences between the observer's and actor's affordances increase. The present study tested those predictions. To do so, observers (participants) made judgments about the farthest distance that an actor (a confederate) could reach. The observer's arms were either free to move or were immobilized by having the participant hold them behind their back. The present results did not support the predictions. The present research introduces a novel means for evaluating the Embodied Simulation Hypothesis, provides initial tests of related predictions, and corroborates prior research. In addition, it motivates important questions about embodied simulation and affordance perception.