The Molecular Basis of Organic Chemiluminescence

Cabello, Maidileyvis Castro; Bartoloni, Fernando Heering; Bastos, E. L.; Baader, W. J.

doi:10.3390/bios13040452

Cited by 20 publications

(8 citation statements)

References 138 publications

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“…There have been several previous computational studies of “charge-transfer-induced luminescence” (CTIL) and variations in timing of charge transfer, O–O, and C–C cleavage. 36 − 38 The extensive and elegant results by Yue and Liu for the adamantyl compound, studied by us as shown in Figure 2 B, showed that the mechanism of dioxetane ring opening involves charge transfer by state crossing during the O–O cleavage transition state. 39 Our activation barrier is very similar to their results with the CAM-B3LYP/6-31G(d) method.…”

Section: Results and Discussionmentioning

confidence: 99%

Spirostrain-Accelerated Chemiexcitation of Dioxetanes Yields Unprecedented Detection Sensitivity in Chemiluminescence Bioassays

Tannous,

Shelef,

Gutkin

et al. 2023

ACS Cent. Sci.

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Chemiluminescence is a fascinating phenomenon that involves the generation of light through chemical reactions. The light emission from adamantyl-phenoxy-1,2-dioxetanes can glow from minutes to hours depending on the specific substituent present on the dioxetane molecule. In order to improve the light emission properties produced by these chemiluminescent luminophores, it is necessary to induce the chemiexcitation rate to a flash mode, wherein the bulk of light is emitted instantly rather than slowly over time. We report the realization of this goal through the incorporation of spirostrain release into the decomposition of 1,2-dioxetane luminophores. DFT computational simulations provided support for the hypothesis that the spiro-cyclobutyl substituent accelerates chemiexcitation as compared to the unstrained adamantyl substituent. Spiro-linking of cyclobutane and oxetane units led to greater than 100-fold and 1000-fold emission enhancement, respectively. This accelerated chemiexcitation rate increases the detection sensitivity for known chemiluminescent probes to the highest signal-to-noise ratio documented to date. A turn-ON probe, containing a spiro-cyclobutyl unit, for detecting the enzyme β-galactosidase exhibited a limit of detection value that is 125-fold more sensitive than that for the previously described adamantyl analogue. This probe was also able to instantly detect and image β-gal activity with enhanced sensitivity in E. coli bacterial assays.

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Section: Results and Discussionmentioning

confidence: 99%

Spirostrain-Accelerated Chemiexcitation of Dioxetanes Yields Unprecedented Detection Sensitivity in Chemiluminescence Bioassays

Tannous,

Shelef,

Gutkin

et al. 2023

ACS Cent. Sci.

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“…By an analogy with the classical kinetic methods [ 32 , 33 ], “Fixed time method” and “Initial rate method” can be used in the potentiometry. The absolute value of the potential cannot be selected as a changeable parameter in the “Initial rate method” because there is no potential pair and the equilibrium of the system is not achieved in the described method.…”

Section: Resultsmentioning

confidence: 99%

Kinetic Potentiometry as a Method for Studying the Interactions of Antioxidants with Peroxyl Radicals

Gerasimova,

Salimgareeva,

Magasumova

et al. 2023

Antioxidants

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This work presents a new method using kinetic potentiometry to study the thermodynamic and kinetic parameters of the reactions of antioxidants with peroxyl radicals. The rate constants of the reaction of antioxidants with radicals have been determined, and the groups of “fast” and “slow” antioxidants have been conventionally distinguished. Fast antioxidants include ascorbic, uric, gallic, chlorogenic, caffeic acids, glutathione, L-cysteine, and catechol with constant values from (1.05–9.25) × 103 M·s−1; “slow” antioxidants are α-tocopherol (in aqueous media), ionol, 2,6-ditretbutylphenol, and compounds of the azoloazine series, modified with polyphenolic fragments, with constant values from (4.00–8.50) × 102 M·s−1. It is shown that the value of the rate constant is directly related to the type of kinetic dependence of the potential recorded when an antioxidant is introduced into the solution of the radical initiator. It is shown that the method with the determination of the induction period is difficult in the study of “slow” antioxidants. It has been established that the area above the curve of the kinetic dependence Exp(∆E) is directly related to the amount of inhibited peroxyl radicals and can be used to assess the inhibitory properties of an antioxidant from a thermodynamic point of view. “Fixed time method” and “Initial rate method” were used. Positive correlations between the described method have been established. The utility of the parameter of the area above the curve of the kinetic dependence Exp(∆E) in the study of objects of complex composition is shown.

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“…78–80 Additionally, they bear a modular scaffold, which can be simply modified toward the development of activity-based probes. Accordingly, new generation 1,2-dioxetane derivatives have been developed to monitor numerous analytes ranging from enzymes to ROS and biothiols including H 2 S. 81–86 Very recently, we have introduced the first ever example of a mitochondria-targeted chemiluminescence agent by modifying the phenoxy 1,2-dioxetane core, which was responsive to the leucine aminopeptidase (LAP) enzyme, with a well-established mitochondrion targeting triphenylphosphonium (TPP) group. 87 Cationic nature of TPP is critical to ensure the attraction between the probe and the negatively charged membrane of mitochondria as previously shown in the literature.…”

Section: Introductionmentioning

confidence: 99%

A mitochondria-targeted chemiluminescent probe for detection of hydrogen sulfide in cancer cells, human serum and in vivo

et al. 2023

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The Molecular Basis of Organic Chemiluminescence

Cited by 20 publications

References 138 publications

Spirostrain-Accelerated Chemiexcitation of Dioxetanes Yields Unprecedented Detection Sensitivity in Chemiluminescence Bioassays

Spirostrain-Accelerated Chemiexcitation of Dioxetanes Yields Unprecedented Detection Sensitivity in Chemiluminescence Bioassays

Kinetic Potentiometry as a Method for Studying the Interactions of Antioxidants with Peroxyl Radicals

A mitochondria-targeted chemiluminescent probe for detection of hydrogen sulfide in cancer cells, human serum and in vivo

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