In Cellulo Peptide Cyclization via Gene‐Encoded Proximity‐Induced Proline‐Isothiocyanate Crosslinking

Z Zhifen Huang (State Key Laboratory of Synthetic Biology School of Life Sciences Faculty of Medicine Tianjin University Tianjin 300072 China) S Shuai Jiang (State Key Laboratory of Chemical Reaction Dynamics and Dalian Coherent Light Source, Dalian Institute of Chemical Physics) J Jiaying Ren (State Key Laboratory of Synthetic Biology School of Life Sciences Faculty of Medicine Tianjin University Tianjin 300072 China) L Lei Zhao (School of Life Sciences, Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, and Hubei Key Laboratory of Genetic Regulation and Integrative Biology, Central China Normal University) Z Zhuo Zhang (College of Chemistry) H Hongqiang Qin G Gong Chen (State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry) W Weimin Xuan (State Key Laboratory of Advanced Fiber Materials & College of Chemistry and Chemical Engineering)

Abstract

Abstract Cyclic peptides represent a very useful modality in modern drug discovery. However, there remain substantial technical challenges in the de novo biosynthesis of complex cyclic peptides particularly in an intracellular manner. Herein, we demonstrate that an isothiocyanate (ITC) group encoded via genetic code expansion could selectively and efficiently crosslink to proximal N‐terminal Pro (P‐ITC crosslinking) and affords cyclic peptides without obvious limitations related to amino acid composition (including Lys and Cys) or sequence length. Notably via P‐ITC crosslinking, a disulfide‐bridged 13‐mer bicyclic peptide is facilely constructed in E. coli , thus lending us the ability to intracellularly construct and select complex cyclic peptides.

Article Details

Volume / Issue Vol. 65, Issue 3
Published January 16, 2026
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (8)

Z

Zhifen Huang

State Key Laboratory of Synthetic Biology School of Life Sciences Faculty of Medicine Tianjin University Tianjin 300072 China

S

Shuai Jiang

State Key Laboratory of Chemical Reaction Dynamics and Dalian Coherent Light Source, Dalian Institute of Chemical Physics

J

Jiaying Ren

State Key Laboratory of Synthetic Biology School of Life Sciences Faculty of Medicine Tianjin University Tianjin 300072 China

L

Lei Zhao

School of Life Sciences, Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, and Hubei Key Laboratory of Genetic Regulation and Integrative Biology, Central China Normal University

Z

Zhuo Zhang

College of Chemistry

H

Hongqiang Qin

G

Gong Chen

State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry

W

Weimin Xuan

State Key Laboratory of Advanced Fiber Materials & College of Chemistry and Chemical Engineering