Rapaprotin, an Endopeptidase‐Activated Proteasome Inhibitor that Induces 26S Disassembly

H Hanjing Peng (Department of Pharmacology and Molecular Sciences Johns Hopkins School of Medicine Baltimore MD 21205 USA) Z Zufeng Guo (Department of Pharmacology and Molecular Sciences Johns Hopkins School of Medicine Baltimore MD 21205 USA) W Wei Li Wang (State Key Laboratory for Artificial Microstructures and Mesoscopic Physics Laboratory of Electron Microscopy School of Physics Peking University Beijing 100871 China) D Deyao Yin (State Key Laboratory for Artificial Microstructures and Mesoscopic Physics Laboratory of Electron Microscopy School of Physics Peking University Beijing 100871 China) S Shitao Zou (State Key Laboratory for Artificial Microstructures and Mesoscopic Physics Laboratory of Electron Microscopy School of Physics Peking University Beijing 100871 China) T Thomas Asbell (Department of Pharmacology and Molecular Sciences Johns Hopkins School of Medicine Baltimore MD 21205 USA) B Brett R. Ullman (Rapafusyn Pharmaceuticals Baltimore MD 21205 USA) M Maya Thakar (Sidney Kimmel Comprehensive Cancer Center Johns Hopkins School of Medicine Baltimore MD 21287 USA) F Feiran Zhang (Department of Chemistry, Mechanical Engineering and School of Biomedical Sciences, The University of Hong Kong) S Sam Y. Hong (Rapafusyn Pharmaceuticals Baltimore MD 21205 USA) A A. V. Subba Rao (Department of Pharmacology and Molecular Sciences Johns Hopkins School of Medicine Baltimore MD 21205 USA) K Kunyu Wang S Shuwen Zhang Z Zhaolong Wu X Xuemei Li (RIKEN Center for Brain Science) A Aidan A. Kendra (Department of Pharmacology and Molecular Sciences Johns Hopkins School of Medicine Baltimore MD 21205 USA) S Seth S. Margolis (Solomon H. Snyder Department of Neuroscience Johns Hopkins School of Medicine Baltimore MD 21205 USA) W William H. Matsui (Sidney Kimmel Comprehensive Cancer Center Johns Hopkins School of Medicine Baltimore MD 21287 USA) C Christian B. Gocke (Sidney Kimmel Comprehensive Cancer Center Johns Hopkins School of Medicine Baltimore MD 21287 USA) Y Youdong Mao J Jun O. Liu

Abstract

Abstract The 19S regulatory particle (RP) associates with the 20S core particle (CP) to form the 26S proteasome, an evolutionarily conserved holoenzyme that plays key roles in both physiological and pathological processes. Proteasome inhibitors that target the catalytic subunits within the 20S have proven to be valuable research tools and therapeutics for various cancers. Herein we report the discovery of rapaprotin, a 26S proteasome assembly inhibitor from our natural product‐inspired hybrid macrocycle rapafucin library. Rapaprotin induces apoptosis in both myeloma and leukemia cell lines. Genome‐wide CRISPR‐Cas9 screen identified a cytosolic enzyme, prolyl endopeptidase (PREP) that is required for the pro‐apoptotic activity of rapaprotin. Further mechanistic studies revealed that rapaprotin acts as a molecular transformer, changing from an inactive cyclic form into an active linear form, rapaprotin‐L, upon PREP cleavage, to block 26S proteasome activity. Time‐resolved cryogenic electron microscopy (cryo‐EM) revealed that rapaprotin‐L induces dissociation of the 19S RP from the 26S holoenzyme, which was verified in cells. Furthermore, rapaprotin exhibits a marked synergistic effect with FDA‐approved proteasome inhibitors and resensitizes drug‐resistant multiple myeloma cells from patients to bortezomib. Taken together, these results suggest that rapaprotin is a new chemical tool to probe the dynamics of the 26S proteasome assembly and a promising anticancer drug lead.

Article Details

Volume / Issue Vol. 64, Issue 46
Published November 10, 2025
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (21)

H

Hanjing Peng

Department of Pharmacology and Molecular Sciences Johns Hopkins School of Medicine Baltimore MD 21205 USA

Z

Zufeng Guo

Department of Pharmacology and Molecular Sciences Johns Hopkins School of Medicine Baltimore MD 21205 USA

W

Wei Li Wang

State Key Laboratory for Artificial Microstructures and Mesoscopic Physics Laboratory of Electron Microscopy School of Physics Peking University Beijing 100871 China

D

Deyao Yin

State Key Laboratory for Artificial Microstructures and Mesoscopic Physics Laboratory of Electron Microscopy School of Physics Peking University Beijing 100871 China

S

Shitao Zou

State Key Laboratory for Artificial Microstructures and Mesoscopic Physics Laboratory of Electron Microscopy School of Physics Peking University Beijing 100871 China

T

Thomas Asbell

Department of Pharmacology and Molecular Sciences Johns Hopkins School of Medicine Baltimore MD 21205 USA

B

Brett R. Ullman

Rapafusyn Pharmaceuticals Baltimore MD 21205 USA

M

Maya Thakar

Sidney Kimmel Comprehensive Cancer Center Johns Hopkins School of Medicine Baltimore MD 21287 USA

F

Feiran Zhang

Department of Chemistry, Mechanical Engineering and School of Biomedical Sciences, The University of Hong Kong

S

Sam Y. Hong

Rapafusyn Pharmaceuticals Baltimore MD 21205 USA

A

A. V. Subba Rao

Department of Pharmacology and Molecular Sciences Johns Hopkins School of Medicine Baltimore MD 21205 USA

K

Kunyu Wang

S

Shuwen Zhang

Z

Zhaolong Wu

X

Xuemei Li

RIKEN Center for Brain Science

A

Aidan A. Kendra

Department of Pharmacology and Molecular Sciences Johns Hopkins School of Medicine Baltimore MD 21205 USA

S

Seth S. Margolis

Solomon H. Snyder Department of Neuroscience Johns Hopkins School of Medicine Baltimore MD 21205 USA

W

William H. Matsui

Sidney Kimmel Comprehensive Cancer Center Johns Hopkins School of Medicine Baltimore MD 21287 USA

C

Christian B. Gocke

Sidney Kimmel Comprehensive Cancer Center Johns Hopkins School of Medicine Baltimore MD 21287 USA

Y

Youdong Mao

J

Jun O. Liu