| Autor: |
Gutkin, Sara, Shelef, Omri, Babjaková, Zuzana, Tomanová, Laura Anna, Babjak, Matej, Kopp, Tal, Zhou, Qingyang, Ma, Pengchen, Fridman, Micha, Spitz, Urs, Houk, Kendall N., Shabat, Doron |
| Zdroj: |
JACS Au; September 2024, Vol. 4 Issue: 9 p3558-3566, 9p |
| Abstrakt: |
The chemiluminescent light-emission pathway of phenoxy-1,2-dioxetane luminophores is increasingly attracting the scientific community’s attention. Dioxetane probes that undergo rapid, flash-type chemiexcitation demonstrate higher detection sensitivity than those with a slower, glow-type chemiexcitation rate. This is primarily because the rapid flash-type produces a greater number of photons within a given time. Herein, we discovered that dioxetanes fused to 7-norbornyl and homocubanyl units present accelerated chemiexcitation rates supported by DFT computational simulations. Specifically, the 7-norbornyl and homocubanyl spirofused dioxetanes exhibited a chemiexcitation rate 14.2-fold and 230-fold faster than that of spiro-adamantyl dioxetane, respectively. A turn-ON dioxetane probe for the detection of the enzyme β-galactosidase, containing the 7-norbornyl spirofused unit, exhibited an S/N value of 415 at a low enzyme concentration. This probe demonstrated an increase in detection sensitivity toward β-galactosidase expressing bacteria E. coliwith a limit-of-detection value that is 12.8-fold more sensitive than that obtained by the adamantyl counterpart. Interestingly, the computed activation free energies of the homocubanyl and 7-norbornyl units were correlated with their CCsC spiro-angle to corroborate the measured chemiexcitation rates. |
| Databáze: |
Supplemental Index |
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