"Gear-driven"-type chirality transfer of tetraphenylethene-based supramolecular organic frameworks for peptides in water

• Published in: Chemical science (Cambridge) Vol. 15; no. 1; pp. 3758 - 3766
• Main Authors: Yan, Chaochao, Li, Qingfang, Wang, Kaige, Yang, Wanni, Han, Jingyu, Li, Yawen, Dong, Yunhong, Chu, Dake, Cheng, Lin, Cao, Liping
• Format: Journal Article
• Language: English
• Published: CAMBRIDGE Royal Soc Chemistry 06.03.2024; Royal Society of Chemistry; The Royal Society of Chemistry
• Subjects: Amino acids; Biomolecules; Chemistry; Chemistry, Multidisciplinary; Chirality; Dichroism; Peptides; Phenylalanine; Physical Sciences; Recognition; Rotational spectra; Science & Technology; Selective binding; Sensor arrays; Structural analysis; Tryptophan; AMPLIFICATION; FLUORESCENCE; RECOGNITION; AGGREGATION-INDUCED EMISSION; PLANAR CHIRALITY; ADAPTIVE CHIRALITY; ACHIRAL CAGE; INDUCTION
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/d3sc06349f

Chirality transfer for natural chiral biomolecules can reveal the indispensable role of chiral structures in life and can be used to develop the chirality-sensing biomolecular recognition. Here, we report the synthesis and characterization of a series of achiral supramolecular organic frameworks ( SOF-1 , SOF-2 , and SOF-3 ), constructed from cucurbit[8]uril (CB[8]) and tetraphenylethene (TPE) derivatives ( 1 , 2 , and 3 ), respectively, as chirality-sensing platforms to explore their chirality transfer mechanism for peptides in water. Given the right-handed ( P ) and left-handed ( M ) rotational conformation of TPE units and the selective binding of CB[8] to aromatic amino acids, these achiral SOFs can be selectively triggered in water by peptides containing N-terminal tryptophan (W) and phenylalanine (F) residues into their P - or M -rotational conformation, exhibiting significantly different circular dichroism (CD) spectra. Although various peptides have the same l -type chiral configuration, they can induce positive CD signals of SOF-1 and negative CD signals of SOF-2 and SOF-3 , respectively. Based on the structural analysis of the linkage units between CB[8] and TPE units in these SOFs, a "gear-driven"-type chirality transfer mechanism has been proposed to visually illustrate the multiple-step chirality transfer process from the recognition site in the CB[8]'s cavity to TPE units. Furthermore, by utilizing the characteristic CD signals generated through the "gear-driven"-type chirality transfer, these SOFs can serve as chiroptical sensor arrays to effectively recognize and distinguish various peptides based on their distinctive CD spectra. A "gear-driven"-type chirality transfer mechanism has been proposed to illustrate the multiple-step chirality transfer of TPE-based supramolecular organic frameworks (SOFs) for peptides.