Quantitative Assessment of Xenon Exchange Kinetics with Cucurbit[6]uril in Physiological Saline

Cucurbit[6]uril and xenon form supramolecular complexes that are of great potential for biosensing by NMR. This host-guest system acts alike a signaler in sensors facilitating the ultrasensitive detection of biomarkers by saturation transfer of chemically exchanging, hyperpolarized ¹²⁹ Xe. Here, the exchange process is evaluated by NMR exchange spectroscopy utilizing the preparation of anti-parallel longitudinal magnetization with respect to free and host-bound xenon and the variation of xenon concentration. Evidence for dissociative as well as degenerate exchange mechanisms is revealed by a linear regression analysis of the determined exchange rates resulting in rate coefficients of 1131±11 s^-1 (2390±70 s^-1 ) and 108500±4900 M^-1  s^-1 (174200±13900 M^-1  s^-1 ), respectively, and an affinity constant of 289±8 M^-1 (278±14 M^-1 ) in physiological saline at 298 K (310 K). The results elucidate the supramolecular exchange and underpin the high efficacy for biosensing of this host-guest system. The approach is generally applicable to enhanced host-xenon exchange dynamics, yet slow on the NMR timescale, for quantitative kinetics and biosensing analyses.