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Proton‐Gradient‐Driven Self‐Assembly of Porphyrin and In Situ Dynamic Analysis in a Microflow Platform
Author(s) -
Kanzaki Chisako,
Inagawa Arinori,
Fukuhara Gaku,
Okada Tetsuo,
Numata Munenori
Publication year - 2020
Publication title -
chemsystemschem
Language(s) - English
Resource type - Journals
ISSN - 2570-4206
DOI - 10.1002/syst.202000006
Subject(s) - laminar flow , nucleation , supramolecular chemistry , porphyrin , dispersity , chemical physics , chemistry , self assembly , proton , protonation , nanotechnology , materials science , molecule , polymer chemistry , thermodynamics , photochemistry , organic chemistry , physics , ion , quantum mechanics
Despite rapid advances in supramolecular chemistry, only limited attention has been paid to regulating the self‐assembling field, such as by studying diffusional dynamics or the hydrodynamic properties of the solvents that always surround the self‐assembling molecules. Herein, we demonstrate that a proton gradient generated in laminar flow can facilitate the acid‐base reaction, leading to effective self‐assembly of TPPS, a type of porphyrin. In situ fluorescence microspectroscopies reveal that the acid‐base reaction followed by self‐assembly of TPPS proceed under a uniform diffusional environment in the laminar flow, leading to the creation of discrete J‐aggregate fibers (length dispersity L w / L n <1.2). Furthermore, we can successfully evaluate the time required for nucleation to be 2.9 ms. In sharp contrast to conventional solution chemistry, the nucleation process of TPPS finishes at a much earlier stage, implying that nucleation might no longer be the rate‐determining step in laminar flow. The present self‐assembly system in laminar flow provides a way to create a variety of supramolecular architectures under reproducible kinetic conditions, and a comprehensive strategy to construct a kinetic database for self‐assembly dynamics.