2026-10-13T10:01:16Z https://api.figshare.com/v2/oai

oai:figshare.com:article/34018586 2026-09-28T22:04:45Z category_1 category_4 category_8 category_14 category_21 category_873 category_135 portal_63 item_type_6 month_year_09_2026

Rigid-Flexible Coupling Pore Engineering in Covalent Organic Frameworks Enables the Selective Identification of Nucleotide Analogues Yizhang Li (8435967) Linjing Tong (11519827) Weiyu Ye (22101644) Rui Gao (247606) Xiaoxue Kou (4855873) Yufan Liang (1314642) Jinsheng Huang (4414897) Siming Huang (4855870) Fang Zhu (185566) Guosheng Chen (2803423) Gangfeng Ouyang (1505890) Biophysics Biochemistry Microbiology Molecular Biology Biotechnology Chemical Sciences not elsewhere classified Computational Biology wide quantitative range steric hindrance effect photoinduced electron transfer including hydrogen bond enable adaptive binding alkoxy chain length multiple weak interactions analogues adenosine monophosphate flexible heptyloxy chain rigid channels limit rigid fe single fe single hydrophobic interactions fe sites adenosine triphosphate adenosine diphosphate work establishes ultimately triggers synergistic coordination strategically varying sensor design selective recognition selective identification response exclusively longstanding challenge fluorescence turn enzymatic pockets designing cof coordination geometry cof skeleton biomimetic paradigm based sensors 99 nm 50 μm 10 nm Covalent organic frameworks (COFs) offer programmable pore architectures and tunable host–guest interactions, yet their rigid channels limit the selective recognition of structurally similar biomoleculesa longstanding challenge in sensor design. Inspired by enzymatic pockets that combine rigid active sites with flexible secondary coordination spheres, we report a rigid-flexible coupling pore engineering strategy that integrates spatially proximal rigid Fe single-atom switches and dynamic alkoxy chains within a light-emitting hydrazone COF scaffold. By strategically varying the alkoxy chain length from methoxy to heptyloxy, we demonstrate that elongated flexible chains modulate the coordination geometry of Fe single-atom sites through steric hindrance effect and enable adaptive binding of adenosine triphosphate (ATP) over its analogues adenosine monophosphate and adenosine diphosphate. This selective recognition, driven by synergistic coordination from the rigid Fe single-atom and multiple weak interactions (including hydrogen bond, C–H···π, and hydrophobic interactions) from the flexible heptyloxy chain, suppresses the photoinduced electron transfer from the COF skeleton to the Fe sites and ultimately triggers a fluorescence turn-on response exclusively for ATP, with a wide quantitative range from 10 nM to 50 μM and a limit of detection as low as 8.99 nM. This work establishes a biomimetic paradigm for designing COF-based sensors with tailored specificity toward structurally similar nucleotides. 2026-09-28T00:00:00Z Text Journal contribution 10.1021/jacs.6c16288.s001 https://figshare.com/articles/journal_contribution/Rigid-Flexible_Coupling_Pore_Engineering_in_Covalent_Organic_Frameworks_Enables_the_Selective_Identification_of_Nucleotide_Analogues/34018586 CC BY-NC 4.0