Encapsulation of xenon by bridged resorcinarene cages with high ¹²⁹Xe NMR chemical shift and efficient exchange dynamics
Komulainen, Sanna; Fernando, P. U. Ashvin Iresh; Mareš, Jiří; Selent, Anne; Khalili, Roya; Cesana, Paul T.; Ebeling, Andreas; Kantola, Anu M.; Beyeh, Ngong Kodiah; Rissanen, Kari; DeBoef, Brenton; Lantto, Perttu; Telkki, Ville-Veikko (2023-02-15)
Komulainen, S., Iresh Fernando, P. U. A., Mareš, J., Selent, A., Khalili, R., Cesana, P. T., Ebeling, A., Kantola, A. M., Beyeh, N. K., Rissanen, K., DeBoef, B., Lantto, P., & Telkki, V.-V. (2023). Encapsulation of xenon by bridged resorcinarene cages with high 129Xe NMR chemical shift and efficient exchange dynamics. Cell Reports Physical Science, 4(2), 101281. https://doi.org/10.1016/j.xcrp.2023.101281
© 2023 The Author(s). This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
https://creativecommons.org/licenses/by/4.0/
https://urn.fi/URN:NBN:fi-fe2023041937639
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Abstract
Functionalized cages encapsulating xenon atoms enable highly sensitive, background-free molecular imaging through a technique known as HyperCEST ¹²⁹Xe MRI. Here, we introduce a class of potential biosensor cage structures based on two resorcinarene macrocycles bridged either by aliphatic carbon chains or piperazines. First-principles-based modeling predicts a high chemical shift (about 345 ppm) outside the typical experimental observation window for ¹²⁹Xe encapsulated by the aliphatically bridged cage and two ¹²⁹Xe resonances for the piperazine-bridged cages corresponding to single and double loading. Based on the computational predictions as well as ¹²⁹Xe chemical exchange saturation transfer (CEST) and T₂ relaxation nuclear magnetic resonance experiments, we confirm Xe encapsulation in the aliphatically bridged and double encapsulation in the piperazine-bridged resorcinarene in methanol. The cages show fast Xe exchange rates (12,000–49,000 s⁻¹), resulting in a high CEST response regardless of the relatively low binding constant (0.09–3 M⁻¹).
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