Localized Supramolecular Peptide Self‐Assembly Directed by Enzyme‐Induced Proton Gradients

• Published in: Angewandte Chemie International Edition 2017-12, Vol.56 (50), p.15984-15988
• Main Authors: Rodon Fores, Jennifer, Martinez Mendez, Miguel Leonardo, Mao, Xiyu, Wagner, Déborah, Schmutz, Marc, Rabineau, Morgane, Lavalle, Philippe, Schaaf, Pierre, Boulmedais, Fouzia, Jierry, Loïc
• Format: Article
• Language: English
• Subjects: Acidic oxides; Alanine; Chemical Sciences; coating; Electrodes; Glucose; Glucose - chemistry; Glucose - metabolism; Glucose oxidase; Glucose Oxidase - chemistry; Glucose Oxidase - metabolism; Horseradish peroxidase; Horseradish Peroxidase - chemistry; Horseradish Peroxidase - metabolism; Immobilization; Macromolecular Substances - chemistry; Macromolecular Substances - metabolism; Material chemistry; Nanofibers; nanostructures; Oxidation; Oxidation-Reduction; Oxygen; Oxygen - chemistry; Oxygen - metabolism; Peptides - chemistry; Peptides - metabolism; Peroxidase; Protons; Redox reactions; Self-assembly; Substrates; supramolecular chemistry; surface chemistry; Surface Properties
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201709029

Electrodes are ideal substrates for surface localized self‐assembly processes. Spatiotemporal control over such processes is generally directed through the release of ions generated by redox reactions occurring specifically at the electrode. The so‐used gradients of ions proved their effectiveness over the last decade but are in essence limited to material‐based electrodes, considerably reducing the scope of applications. Herein is described a strategy to enzymatically generate proton gradients from non‐conductive surfaces. In the presence of oxygen, immobilization of glucose oxidase (GOx) on a multilayer film provides a flow of protons through enzymatic oxidation of glucose by GOx. The confined acidic environment located at the solid–liquid interface allows the self‐assembly of Fmoc‐AA‐OH (Fmoc=fluorenylmethyloxycarbonyl and A=alanine) dipeptides into β‐sheet nanofibers exclusively from and near the surface. In the absence of oxygen, a multilayer nanoreactor containing GOx and horseradish peroxidase (HRP) similarly induces Fmoc‐AA‐OH self‐assembly. The power of enzymes: A multilayer film including a bi‐enzyme reaction system establishes a proton gradient going from the bottom to the top of the film, leading to the localized self‐assembly of peptides that underpin a supramolecular hydrogel. This approach constitutes an alternative to an electrode surface to induce pH‐sensitive self‐assembly processes.