A1 Journal article (refereed)
Encapsulation of xenon by bridged resorcinarene cages with high 129Xe NMR chemical shift and efficient exchange dynamics (2023)

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), Article 101281. https://doi.org/10.1016/j.xcrp.2023.101281

JYU authors or editors

Publication details

All authors or editors: Komulainen, Sanna; Iresh Fernando, P. U. Ashvin; Mareš, Jiří; Selent, Anne; Khalili, Roya; Cesana, Paul T.; Ebeling, Andreas; Kantola, Anu M.; Beyeh, Ngong Kodiah; Rissanen, Kari; et al.

Journal or series: Cell Reports Physical Science

eISSN: 2666-3864

Publication year: 2023

Publication date: 08/02/2023

Volume: 4

Issue number: 2

Article number: 101281

Publisher: Elsevier

Publication country: United States

Publication language: English

DOI: https://doi.org/10.1016/j.xcrp.2023.101281

Publication open access: Openly available

Publication channel open access: Open Access channel

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/85668

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).

Keywords: supramolecular chemistry; biosensors; xenon; molecular dynamics; computational chemistry

Free keywords: supermolecules; functionalized cages; biosensors; piperazine-bridged resorcinarenes; aliphatically bridged resorcinarenes; 129Xe NMR; 129Xe HyperCEST MRI; first principal modeling; molecular dynamic simulations

Contributing organizations

Ministry reporting: Yes

VIRTA submission year: 2023

JUFO rating: 1