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Isolating Reactions at the Picoliter Scale: Parallel Control of Reaction Kinetics at the Liquid–Liquid Interface
Author(s) -
PhanQuang Gia Chuong,
Lee Hiang Kwee,
Ling Xing Yi
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201602565
Subject(s) - chemistry , liquid liquid , emulsion , kinetics , nanoscopic scale , raman spectroscopy , decane , in situ , chemical engineering , reaction rate constant , protonation , solubility , chemical kinetics , nanotechnology , materials science , organic chemistry , chromatography , physics , engineering , quantum mechanics , optics , ion
Miniaturized liquid–liquid interfacial reactors offer enhanced surface area and rapid confinement of compounds of opposite solubility, yet they are unable to provide in situ reaction monitoring at a molecular level at the interface. A picoreactor operative at the liquid–liquid interface is described, comprising plasmonic colloidosomes containing Ag octahedra strategically assembled at the water‐in‐decane emulsion interface. The plasmonic colloidosomes isolate ultrasmall amounts of solutions (<200 pL), allowing parallel monitoring of multiple reactions simultaneously. Using the surface‐enhanced Raman spectroscopy (SERS) technique, in situ monitoring of the interfacial protonation of dimethyl yellow ( p ‐dimethylaminoazobenzene (DY)) is performed, revealing an apparent rate constant of 0.09 min −1 for the first‐order reaction. The presence of isomeric products with similar physical properties is resolved, which would otherwise be indiscernible by other analytical methods.