Enzyme-Mediated Kinetic Control of Fe³⁺–Tannic Acid Complexation for Interface Engineering

Abstract

Supramolecular self-assembly of Fe 3+ and tannic acid (TA) has received great attention in the fields of materials science and interface engineering because of its exceptional surface coating properties. Although advances in coating strategies often suggest that kinetics in the generation of interface-active Fe 3+ -TA species is deeply involved in the film formation, there is no acceptable elucidation for the coating process. In this work, we developed the enzyme-mediated kinetic control of Fe 2+ oxidation to Fe 3+ in a Fe 2+ -TA complex in the iron-gall-ink-revisited coating method. Specifically, hydrogen peroxide, produced in the glucose oxidase (GOx)catalyzed reaction of D-glucose, accelerated Fe 2+ oxidation, and the optimized kinetics profoundly facilitated the film formation to be about 9 times thicker. We also proposed a perspective considering the coating process as nucleation and growth. From this viewpoint, the kinetics in the generation of interface-active Fe 3+ -TA species should be optimized because it determines whether the interface-active species forms a film on the substrate (i.e., heterogeneous nucleation and film growth) or flocculates in solution (i.e., homogeneous nucleation and particle growth). Moreover, GOx was concomitantly embedded into the Fe 3+ -TA films with sustained catalytic activities, and the GOx-mediated coating system was delightfully adapted to catalytic single-cell nanoencapsulation.

Enzyme‐Instructed Self‐Assembly of Peptides: From Concept to Representative Applications

“…It is therefore required to explore the novel reactions by using the enzyme outside of the protease family. Enzymatic oxidation is a typical candidate for eliciting the self‐assembly, considering some reports demonstrated that the self‐assembly is induced via enzymatic oxidation [22a,b] . Being integrated with the self‐assembly, enzymatic oxidation would facilitate the development of the assemblies with prominent physicochemical properties [83]…”

Hydrogen Bonding‐Based Layer‐by‐Layer Assembly of Nature‐Derived Eggshell Membrane Hydrolysates and Coffee Melanoidins in Single‐Cell Nanoencapsulation

“…SCNE has recently advanced to catalytic SCNE, [51,[67][68][69][70] in which cells are empowered in function by external enzymes and chemical catalysts present in or on the shell, and the biochemical pathways of the cells could be rewired or reprogramed by coupling between innate and external reactions. [1] ESMHs or CMs per se could act as a catalyst due to diverse functional groups.…”

Nanostructured particles assembled from natural building blocks for advanced therapies

“…For example, the kinetics of MPN film formation could be readily tuned by the glucose oxidase-catalyzed reaction of d -glucose, which produces hydrogen peroxide to accelerate the oxidation of Fe 2+ to Fe 3+ in MPN films composed of Fe III –TA complexes. 352 The optimized kinetics of generating Fe 3+ –TA species facilitated film formation, producing MPN films with 9 times higher thickness compared to the air oxidation-based method. In another example, tyrosinase was used to expand the toolbox for MPN assembly by converting monophenol groups of molecules to catechol groups.…”