JACS Au, Год журнала: 2024, Номер 4(11), С. 4488 - 4495
Опубликована: Окт. 22, 2024
The fleeting existence of aryl carbanion intermediates in the bulk phase prevents their direct observation and spectroscopic measurement. In sharp contrast, we report interception such unstable species at air-water interface microdroplets. We observed transformation three types acids (benzoic, phenylsulfinic, phenylboronic acids) into phenyl (Ph
Язык: Английский
Journal of the American Chemical Society, Год журнала: 2024, Номер 146(46), С. 31585 - 31596
Опубликована: Ноя. 12, 2024
Often, chemical reactions are markedly accelerated in microdroplets compared with the corresponding bulk phase. While identifying precise causative factors remains challenging, interfacial electric field (IEF) and partial solvation two widely proposed factors, accounting for acceleration or turning on of many microdroplets. In sharp contrast, this combined computational experimental study demonstrates that these critical have a negligible effect promoting model Diels-Alder (DA) reaction between cyclopentadiene acrylonitrile water Instead, DA appears to be driven by confinement concentration increase caused evaporation. Quantum calculations ab initio molecular dynamics simulations coupled enhanced sampling techniques predict air-water interface exhibits higher free-energy barrier than bulk, while external fields marginally reduce barrier. Remarkably, catalytic capability IEF at microdroplet surface is largely hampered its fluctuating character. Mass spectrometric assessment corroborates findings, suggesting not facilitated as increasing spray potential suppresses products substrate oxidation. preference microdroplets, same tends occur mainly within core acetonitrile microdroplet, necessarily factor accelerating Moreover, experiments indicate rapid evaporation subsequent reagent enrichment accessible confined volume observed
Язык: Английский
Процитировано
6
Analytica Chimica Acta, Год журнала: 2025, Номер 1349, С. 343854 - 343854
Опубликована: Фев. 22, 2025
Язык: Английский
Процитировано
0
Analytical Chemistry, Год журнала: 2025, Номер unknown
Опубликована: Апрель 30, 2025
Язык: Английский
Процитировано
0
JACS Au, Год журнала: 2024, Номер 4(11), С. 4141 - 4147
Опубликована: Ноя. 1, 2024
Water has made Earth a habitable planet by electrifying the troposphere. For example, lightning caused electrification and discharge of cloudwater microdroplets is closely related to atmospheric chemistry. Recent work revealed that high electric field exists at interface water microdroplets, which ∼3 orders magnitude higher than accounts for lightning. A surge exotic redox reactions were recently found over can be contributed such an interfacial field. However, role net charge in microdroplet chemistry should not ignored. In this Perspective, we show how driven electron transfer pathways process microdroplets. Understanding harnessing origin evolution charged are likely lead paradigm shift electrochemistry, may play overlooked geological environmental
Язык: Английский
Процитировано
2
JACS Au, Год журнала: 2024, Номер 4(11), С. 4488 - 4495
Опубликована: Окт. 22, 2024
The fleeting existence of aryl carbanion intermediates in the bulk phase prevents their direct observation and spectroscopic measurement. In sharp contrast, we report interception such unstable species at air-water interface microdroplets. We observed transformation three types acids (benzoic, phenylsulfinic, phenylboronic acids) into phenyl (Ph
Язык: Английский
Процитировано
0