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1.
Chemistry ; 30(14): e202304105, 2024 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-38109441

RESUMO

Commercial zinc metal powder requires activation for consistent and reliable use as a reductant in the formation of organozinc reagents from organohalides, and for the avoidance of supplier and batch-to-batch variability. However, the impact of activation methods on the reaction environments of subsequent intermediates has been unknown. Herein, a fluorescence lifetime imaging microscopy (FLIM) method is developed to bridge this knowledge gap, by imaging and examining reaction intermediates on zinc metal that has been activated by pretreatment through different common methods (i. e., by chemical activation with TMSCl, dibromoethane, or HCl; or by mechanical activation). The group of chemical activating agents, previously thought to act similarly by removing oxide layers, are here shown to produce markedly different reaction environments experienced by subsequent oxidative-addition intermediates from organohalides - data uniquely available through FLIM's ability to detect small quantities of intermediates in situ coupled with its microenvironmental sensitivity. These different microenvironments potentially give rise to different rates of formation, subsequent solubilization, and reactivity, despite the shared "[RZnX]" molecular structure of these intermediates. This information revises models for methods development for oxidative addition to currently sluggish metals beyond zinc by establishing diverse outcomes for pretreatment activation methods that were previously considered similar.

2.
Iperception ; 13(3): 20416695221107391, 2022 May.
Artigo em Inglês | MEDLINE | ID: mdl-35782826

RESUMO

To reduce the spread of COVID-19, mask wearing has become ubiquitous in much of the world. We studied the extent to which masks impair emotion recognition and dampen the perceived intensity of facial expressions by naturalistically inducing positive, neutral, and negative emotions in individuals while they were masked and unmasked. Two groups of online participants rated the emotional intensity of each presented image. One group rated full faces (N=104); the other (N=102) rated cropped images where only the upper face was visible. We found that masks impaired the recognition of and rated intensity of positive emotions. This happened even when the faces were cropped and the lower part of the face was not visible. Masks may thus reduce positive emotion and/or expressivity of positive emotion. However, perception of negativity was unaffected by masking, perhaps because unlike positive emotions like happiness which are signaled more in the mouth, negative emotions like anger rely more on the upper face.

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