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Chaperone-Assisted Host–Guest Interactions Revealed by Single-Molecule Force Spectroscopy

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journal contribution
posted on 08.11.2019, 20:43 by Shankar Pandey, Dilanka V. D. Walpita Kankanamalage, Xiao Zhou, Changpeng Hu, Lyle Isaacs, Janarthanan Jayawickramarajah, Hanbin Mao
The recent discovery of ultra-high binding affinities in cucurbit[7]­uril (CB7)-based host–guest pairs in an aqueous environment has rendered CB7 a rather attractive material in analytical and biomedical applications. Due to the lack of a molecular platform that can follow the same host–guest complex during repetitive mechanical measurements, however, mechanical stabilities of the CB7 system have not been revealed, hindering its potential to rival widely used conjugation pairs, such as streptavidin–biotin. Here, we assembled a DNA template in which a flexible DNA linker was exploited to keep the host (CB7) and guest (adamantane) in proximity. This platform not only increased the efficiency of the single-molecule characterization in optical tweezers but also clearly revealed mechanical features of the same host–guest complex. We found that positively charged adamantane guest demonstrated higher mechanical stability (49 pN) than neutral adamantane (44 pN), a trend consistent with the chemical affinity between guest molecules and the CB7 host. Surprisingly, we found that a hexyl group adjacent to the adamantane served as a chaperone to assist the formation of the adamantane–CB7 pairs. The discovery of an unprecedented chaperone-assisted interaction mechanism provides new approaches to efficiently assemble host–guest-based supramolecules with increased mechanical stabilities, which can be exploited in various biomedical, biosensing, and materials fields.

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