A Photo‐Switchable Peptide Fibril Esterase

Angewandte Chemie, vol. 137

Abstract

Abstract Recent attempts to mimic enzyme catalysis using simple, short peptides have been successful in enhancing various reactions, but the on‐demand, temporal or spatial regulation of such processes by external triggers remains a great challenge. Light irradiation is an ideal trigger for regulating molecular functionality, since it can be precisely manipulated in time and space, and because most reaction mediums do not react to light. We herein report the selection of a photo‐switchable amphiphilic peptide catalyst from a small library of isomeric peptides, each containing an azobenzene‐based light responsive group and a catalytic histidine residue. In its native fibrillar form, the selected peptide is efficiently and enantio‐selectively active for ester hydrolysis, but after irradiation by UV light inducing trans‐to‐cis azobenzene isomerization, the fibrils disassemble to amorphous aggregates that are much less catalytically active. Significantly, this esterase‐like activity can be manipulated multiple times, as the fibrillar peptide assembly is reversibly reduced and restored upon alternate irradiation by UV and visible light, respectively. We propose that this research may shine light on the origin of complex functions in early chemical evolution. Furthermore, it paves the way to regulate additional functions for peptide nanotechnology, such as replication, charge transfer, and delivery.

Authors 11

1. Mousumi Samanta

   Ben-Gurion University of the Negev · Indian Institute of Technology Delhi

   Affiliation as printed

   Chemistry Department Ben-Gurion University of the Negev Campus st. 1 Beer Sheva 8410501 Israel

   Current address: Department of Chemistry Indian Institute of Technology New Delhi 110016 India

2. Noy Saad

   Ben-Gurion University of the Negev

   Affiliation as printed

   Chemistry Department Ben-Gurion University of the Negev Campus st. 1 Beer Sheva 8410501 Israel

3. Dinghao Wu Aachen

   Leiden University

   Affiliation as printed

   Supramolecular & Biomaterials Chemistry Leiden Institute of Chemistry Leiden University 2333CC Leiden, The Netherlands

4. Niek S. A. Crone Aachen

   Leiden University

   Affiliation as printed

   Supramolecular & Biomaterials Chemistry Leiden Institute of Chemistry Leiden University 2333CC Leiden, The Netherlands

5. Karina Abramov Harpaz

   Ben-Gurion University of the Negev

   Affiliation as printed

   Chemistry Department Ben-Gurion University of the Negev Campus st. 1 Beer Sheva 8410501 Israel

6. Clil Regev

   Ben-Gurion University of the Negev

   Affiliation as printed

   Chemistry Department Ben-Gurion University of the Negev Campus st. 1 Beer Sheva 8410501 Israel

7. Rivka Cohen‐Luria

   Ben-Gurion University of the Negev

   Affiliation as printed

   Chemistry Department Ben-Gurion University of the Negev Campus st. 1 Beer Sheva 8410501 Israel

8. Aimee L. Boyle Aachen

   Leiden University · University of Bristol

   Affiliation as printed

   Current address: School of Chemistry University of Bristol Cantock's Close Bristol BS8 1TS UK

   Macromolecular Biochemistry Leiden Institute of Chemistry Leiden University 2333CC Leiden, The Netherlands

9. Yifat Miller

   Ben-Gurion University of the Negev

   Affiliation as printed

   Chemistry Department Ben-Gurion University of the Negev Campus st. 1 Beer Sheva 8410501 Israel

10. Alexander Kros Aachen

    Leiden University

    Affiliation as printed

    Supramolecular & Biomaterials Chemistry Leiden Institute of Chemistry Leiden University 2333CC Leiden, The Netherlands

11. Gonen Ashkenasy

    Ben-Gurion University of the Negev

    Affiliation as printed

    Chemistry Department Ben-Gurion University of the Negev Campus st. 1 Beer Sheva 8410501 Israel