A rhythmic assembly system with fireflies' function based on reversible formation of dynamic covalent bonds driven by a pH oscillator

Abstract

A rhythmic assembly system with fireflies' function driven by a pH oscillator was constructed through the reversible formation of dynamic covalent bonds.

Controlling pH‐Sensitive Chemical Reactions Pathways with Light ‐ a Tale of Two Photobases: an Arrhenius and a Brønsted

“…Based on the results of the first part, in the second part of the study, we used our dual photobase system, enabling the manipulation of pH, to direct the reactions of Alizarin Red S (ARS). ARS can form a complex with phenylboronic acid (PBA) [40,47] or Ni(II) [42] (Scheme 2). Both reactions are fast and can be monitored by spectroscopy owing to the characteristic emission band at 580 nm of the ARS-PBA complex (Figure S6) and the characteristic absorption band at 540 nm of the ARS-Ni (non-emitting) complex (Figure S7).…”

“…ARS is known to undergo different reactions, either with phenylboronic acid (PBA) or Ni(II), which are pH-sensitive and can be monitored using spectroscopy. [40][41][42] Since the two reactions have an opposite pH response, we could direct ARS toward each pathway using our system of two photobases. Altogether, the new concepts we introduce here can be used both for the fundamental understanding of the mechanism of photobases as well as their utilization in various systems.…”

“…Here, we use our new approach for pH control, which results in directing the reaction pathways of ARS. ARS is known to undergo different reactions, either with phenylboronic acid (PBA) or Ni(II), which are pH‐sensitive and can be monitored using spectroscopy [40–42] . Since the two reactions have an opposite pH response, we could direct ARS toward each pathway using our system of two photobases.…”

Functional Rhythmic Chemical Systems Governed by pH‐Driven Kinetic Feedback

“…In terms of potential applications, several promising new directions have appeared in the past years, which go beyond the simple volume-phase transition phenomena: using coloroscillating, [68,107] and protein hydrogels; [51] designing anisotropic and heterogenous hydrogels to get the desired type of motion for actuators (e. g., bending and stretching, bilayers, grippers); [59,67] and driving of periodic dynamic covalent bond formation between phenylboronic acid moieties and 1,2-or 1,3diol moieties. [60][61][62] Recently, Novakovic and Isakova invented a patent on oscillatory gels driven by an oscillatory reaction within the gel. [108] They suggest using a palladium-catalyzed oxidative carbonylation reaction that shows oscillations in pH between 2 and 5.…”

Modulation Effects of Permanganate and Manganese(II) Ions on the Oscillatory Dynamics in a Bromate–Sulfite Reaction System

“…In addition, pH oscillators have many practical applications due to periodical changes in pH values. For example, they can be used as driving elements not only to realize the transformation from the chemical energy of reaction systems to the mechanical work of pH responsive gels , but also to design drug delivery systems. , More recently, research has been focused on the use of pH oscillators to control nanoparticle , and molecular self-assembly processes. − In pH-sensitive biochemical processes, pH oscillations could switch the conformation of DNA structures between folded and random coil states. , …”