Assembly-enhanced recognition: A biomimetic pathway to achieve ultrahigh affinities

F Fang-Yuan Chen (College of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Key Laboratory of Functional Polymer Materials (Ministry of Education), Frontiers Science Center for New Organic Matter, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University) W Wen-Chao Geng (College of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Key Laboratory of Functional Polymer Materials (Ministry of Education), Frontiers Science Center for New Organic Matter, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University) M Meng-Meng Chen (College of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Key Laboratory of Functional Polymer Materials (Ministry of Education), Frontiers Science Center for New Organic Matter, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University) R Rong Fu (Optogenetics & Synthetic Biology Interdisciplinary Research Center, Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism, School of Pharmacy, East China University of Science and Technology, 130 Mei Long Road, Shanghai 200237, China) H Han Han (Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States) Z Zhan-Zhan Zhang (School of Medical Imaging, Tianjin Medical University) W Wen-Bo Li (College of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Key Laboratory of Functional Polymer Materials (Ministry of Education), Frontiers Science Center for New Organic Matter, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University) Y Yuan-Qiu Cheng (College of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Key Laboratory of Functional Polymer Materials (Ministry of Education), Frontiers Science Center for New Organic Matter, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University) J Juan-Juan Li (College of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Key Laboratory of Functional Polymer Materials (Ministry of Education), Frontiers Science and Engineering) J J. Fraser Stoddart K Kang Cai (College of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, Nankai University, 94 Weijin Road, Nankai District, Tianjin 300071, China) D Dong-Sheng Guo (Key Laboratory of Functional Polymer Materials (Ministry of Education), Collaborative Innovation Center of Chemical Science and Engineering, State Key Laboratory of Elemento-Organic Chemistry)

Abstract

On the one hand, nature utilizes hierarchical assemblies to create complex biological binding pockets, enabling ultrastrong recognition toward substrates in aqueous solutions. On the other hand, chemists have been fervently pursuing high-affinity recognition by constructing covalently well-preorganized stereoelectronic cavities. The potential of noncovalent assembly, however, for enhancing molecular recognition has long been underestimated. Inspired by (strept)avidin, an amphiphilic azocalix[4]arene derivative capable of assembly in aqueous solutions has been explored by us and demonstrated to exhibit ultrahigh binding affinity (up to 10 12 M −1 ), which is almost four orders of magnitude higher than those reported for nonassembled azocalix[4]arenes. An ultrastable azocalix[4]arene/photosensitizer complex has been applied in hypoxia-targeted photodynamic therapy for tumors. These findings highlight the immense potential of an assembly-enhanced recognition strategy in the development of the next generation of artificial receptors with appropriate functionalities and extraordinary recognition properties.

Article Details

Volume / Issue Vol. 122, Issue 3
Published January 21, 2025
ISSN 0027-8424
Publisher National Academy of Sciences

Authors (12)

F

Fang-Yuan Chen

College of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Key Laboratory of Functional Polymer Materials (Ministry of Education), Frontiers Science Center for New Organic Matter, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University

W

Wen-Chao Geng

College of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Key Laboratory of Functional Polymer Materials (Ministry of Education), Frontiers Science Center for New Organic Matter, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University

M

Meng-Meng Chen

College of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Key Laboratory of Functional Polymer Materials (Ministry of Education), Frontiers Science Center for New Organic Matter, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University

R

Rong Fu

Optogenetics & Synthetic Biology Interdisciplinary Research Center, Shanghai Frontiers Science Center of Optogenetic Techniques for Cell Metabolism, School of Pharmacy, East China University of Science and Technology, 130 Mei Long Road, Shanghai 200237, China

H

Han Han

Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States

Z

Zhan-Zhan Zhang

School of Medical Imaging, Tianjin Medical University

W

Wen-Bo Li

College of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Key Laboratory of Functional Polymer Materials (Ministry of Education), Frontiers Science Center for New Organic Matter, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University

Y

Yuan-Qiu Cheng

College of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Key Laboratory of Functional Polymer Materials (Ministry of Education), Frontiers Science Center for New Organic Matter, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University

J

Juan-Juan Li

College of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Key Laboratory of Functional Polymer Materials (Ministry of Education), Frontiers Science and Engineering

J

J. Fraser Stoddart

K

Kang Cai

College of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, Nankai University, 94 Weijin Road, Nankai District, Tianjin 300071, China

D

Dong-Sheng Guo

Key Laboratory of Functional Polymer Materials (Ministry of Education), Collaborative Innovation Center of Chemical Science and Engineering, State Key Laboratory of Elemento-Organic Chemistry