Probing Oxygen Transport in β-Cyclodextrin–Cyclohexane Crystalline Nanochannels by Luminescence Quenching from Nanoseconds to Seconds
- 1NRC “Kurchatov Institute, Academician Kurchatov sq. 1, Moscow, Russia, 123182
- 2Moscow Institute of Physics and Technology, Institutskiy per. 9, Dolgoprudny, Moscow Region, Russian Federation, 141701
- 3A.N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences, Vavilova St., 28, bld. 1., Moscow, Russian Federation, 119334
Abstract
Molecular transport in supramolecular crystals under nanoscale confinement may exhibit different regimes across widely separated timescales, making their experimental characterization particularly challenging. Here, oxygen quenching of aromatic luminophores incorporated into a β -cyclodextrin–cyclohexane crystalline matrix in aqueous suspensions is investigated using steadystate and time-resolved luminescence spectroscopy. The probes provide emission lifetimes ranging from tens of nanoseconds to approximately 15 s. Effective bimolecular quenching rate constants referenced to the concentration of dissolved oxygen in the surrounding aqueous phase decrease from approximately 10 9 to 5×10 4 L mol -1 s -1 across the probe series. The decreasing branch approximately follows a power-law dependence on the unquenched emission lifetime, k q ∝ τ 0 -0.8 , whereas probes with lifetimes longer than approximately 10 ms exhibit a nearly constant quenching rate. A diffusion–reaction model relates the measured constants to temporal averages of the oxygen encounter flux and accounts for the finite excitation duration. Under the assumptions of comparable probe accessibility and diffusion-controlled quenching, the observed scaling is consistent with subdiffusive transport with an effective anomalous exponent of approximately 0.4. A finite range of local transition rates within a quenched random-barrier model provides a possible explanation for the crossover to the long-time plateau. These results show that lifetime-dependent luminescence quenching provides a means of probing oxygen transport over widely separated timescales and testing transport models in nanoscale-confined molecular systems.
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BibTeX
@misc{makhrov2026probing,
title = {{Probing Oxygen Transport in β-Cyclodextrin–Cyclohexane Crystalline Nanochannels by Luminescence Quenching from Nanoseconds to Seconds}},
author = {Denis E. Makhrov and Irina V. Ionova and Alexander A. Korlyukov and Alexander D. Volodin and Georgy A. Yurasik and Mikhail V. Alfimov and Dmitriy S. Ionov},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15009739/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009739/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Probing Oxygen Transport in β-Cyclodextrin–Cyclohexane Crystalline Nanochannels by Luminescence Quenching from Nanoseconds to Seconds
AU - Denis E. Makhrov
AU - Irina V. Ionova
AU - Alexander A. Korlyukov
AU - Alexander D. Volodin
AU - Georgy A. Yurasik
AU - Mikhail V. Alfimov
AU - Dmitriy S. Ionov
PY - 2026
DA - 2026/10/01
PB - ChemRxiv
DO - 10.26434/chemrxiv.15009739/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009739/v1
AB - Molecular transport in supramolecular crystals under nanoscale confinement may exhibit different regimes across widely separated timescales, making their experimental characterization particularly challenging. Here, oxygen quenching of aromatic luminophores incorporated into a β -cyclodextrin–cyclohexane crystalline matrix in aqueous suspensions is investigated using steadystate and time-resolved luminescence spectroscopy. The probes provide emission lifetimes ranging from tens of nanoseconds to approximately 15 s. Effective bimolecular quenching rate constants referenced to the concentration of dissolved oxygen in the surrounding aqueous phase decrease from approximately 10 9 to 5×10 4 L mol -1 s -1 across the probe series. The decreasing branch approximately follows a power-law dependence on the unquenched emission lifetime, k q ∝ τ 0 -0.8 , whereas probes with lifetimes longer than approximately 10 ms exhibit a nearly constant quenching rate. A diffusion–reaction model relates the measured constants to temporal averages of the oxygen encounter flux and accounts for the finite excitation duration. Under the assumptions of comparable probe accessibility and diffusion-controlled quenching, the observed scaling is consistent with subdiffusive transport with an effective anomalous exponent of approximately 0.4. A finite range of local transition rates within a quenched random-barrier model provides a possible explanation for the crossover to the long-time plateau. These results show that lifetime-dependent luminescence quenching provides a means of probing oxygen transport over widely separated timescales and testing transport models in nanoscale-confined molecular systems.
ER -