Abstract
In this study, we investigated a unique aspect of the supramolecular polymerization of tetrakis (4-sulfonatophenyl) porphyrin (TPPS), a self-assembling porphyrin, under non-equilibrium conditions by subtracting the effects of back-pressure on its polymerization. We focused on the enhanced self-assembly abilities of TPPS under a process of rapid proton diffusion in a microflow channel. Rapid protonation caused synchronization of many sets of protonation/deprotonation equilibria on the molecular scale, leading to the production of many sets of growing suparmolecular spices. Pressure effects in the microflow channel, which could potentially promote self-assembly of TPPS, were negligible, becoming predominant only when the system was in the synchronized state.
Highlights
Anomalous amplification of weak interactions through synchronized behavior of components is ubiquitous in Nature on many scales, from elementary particles to the global scale
The time required for proton diffusion was directly correlated to the width of the central flow, which we could control through the flow rate—a faster flow led to a narrower width (Figures 3b and 4a)
Back-pressure has, in essence, a negligible effect on the self-assembly; it appeared only when H4TPPS was temporally concentrated through rapid protonation
Summary
Anomalous amplification of weak interactions through synchronized behavior of components is ubiquitous in Nature on many scales, from elementary particles to the global scale. We proposed the possibility that molecules could be synchronized under very rapid environmental changes (e.g., pH or solvent polarity) in flowing micro-solutions [1,2]. Those results were very primitive, we established simple models for chemists to consider the synchronized behaviors of molecules. We have employed tetrakis (4-sulfonatophenyl) porphyrin (TPPS, with H2 TPPS and H4 TPPS representing its free and protonated forms, respectively) as a model compound for such studies (Figure 1) [3,4,5,6,7,8]. J-aggregates formation is triggered by protonation of the central pyrrole groups
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