Constructing the Mechanism of Dinoflagellate Luciferin Bioluminescence Using Computation

Phun, Gabriel S.; Rappoport, Dmitrij; Furche, Filipp; Nelson, Tammie; Tretiak, Sergei

doi:10.1021/acs.jpclett.3c01053

Cited by 3 publications

(3 citation statements)

References 68 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Second, the dissociation stage is crucial for the generation of a light emitter. 24,25 The anionic DHD − formed by the oxidation could interconvert with neutral DHD in the phosphate buffer solution (PBS), but the dissociation mechanism of DHD − and DHD has not been clearly explored in our previous studies. Additionally, we do not know what is the effect of the relative proportions of DHD/ DHD − in the solution on the CL.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Investigation into Chemiluminescence from 1,4-Benzoquinone

Quan,

Liu

2024

J. Phys. Chem. A

View full text Add to dashboard Cite

Tetrahalogen-1,4-benzoquinone (THBQ) represents a category of H 2 O 2 -dependent substrates for chemiluminescence (CL), including tetrafluoro-, tetrachloro-, tetrabromo-, and tetraiodo-1,4-benzoquinone (TFBQ, TCBQ, TBBQ, and TIBQ). A deep understanding of the CL mechanism of THBQ is essential for all H 2 O 2 -dependent CL and even some bioluminescence. This article systematically investigates the CL process of THBQ by density functional theory and multireference state theory. The theoretical results confirm the generality of the CL mechanism previously proposed in studies on TCBQ and TBBQ. The dissociation steps producing the emitter of light from dihalogenquinone dioxetane (DHD) and its anion (DHD − ), formed by the oxidation of THBQ, were carefully considered. Findings show that the dissociation of DHD/DHD − follows the entropy trap/gradually reversible charge-transfer-induced luminescence (GRCTIL) mechanisms. The dissociation of DHD − is kinetically more advantageous compared with that of DHD. At the practical experimental pH value, the decrease in the electron-withdrawing inductive effect from F to I substituents results in the decrease in the proportions of easily dissociated DHD − , and the increase in the heavy-atom effect from F to I substituents leads to the increase in the phosphorescence emission. These combined factors successively decrease the CL intensity from TFBQ to TCBQ, TBBQ, and TIBQ. The conclusions are verified by the previous experiments on TCBQ and TBBQ, and they are expected to be confirmed by future experiments on TFBQ and TIBQ.

show abstract

Section: Introductionmentioning

confidence: 99%

Mechanistic Investigation into Chemiluminescence from 1,4-Benzoquinone

Quan,

Liu

2024

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

“…Since obtaining and elucidating the structure, as well as achieving the synthesis of the luciferin substrate (LUC, Scheme ) by Bitler et al and White et al in the late 1950s, , extensive experimental and theoretical research has been conducted to understand the mechanism involved in the efficient bioluminescence (BL) of Photinus pyralis. , The study of BL in general benefits from computational simulations of entire systems, − as well as from working with chemiluminescence (CL) reactions that serve as comprehensive models and analogues of BL processes. , …”

Section: Introductionmentioning

confidence: 99%

Chemiluminescence of a Firefly Luciferin Analogue Reveals that Formation of the Key Intermediate Responsible for Excited State Generation Occurs on a Fully Concerted Step

Melo,

Bergonzini de Lima,

Reis

et al. 2023

J. Org. Chem.

View full text Add to dashboard Cite

The chemiluminescence (CL) reaction of eight different 2-(4-hydroxyphenyl)-4,5-dihydrothiazole-4-carboxylate esters with an organic superbase and oxygen was investigated through a kinetic and computational study. These esters are all analogues to the luciferin substrate involved in efficient firefly bioluminescence. The kinetic data obtained from CL emission and light absorption assays were used in the context of linear free energy relationships (LFER); we obtained the Hammett reaction constant ρ = +1.62 ± 0.09 and the Brønsted constant β lg = −0.39 ± 0.04. These observations from LFER, together with activation parameters obtained from Arrhenius plots, suggest that the formation of the high-energy intermediate (HEI) 1,2-dioxetanone occurs via a concerted mechanism during the rate-determining step of the reaction. Calculations performed using density functional theory support a late transition state for HEI formation within the reaction mechanism pathway, which was described considering geometric parameters, Wiberg bond indices from natural bond order analysis, and the atomic charges derived from the electrostatic potential.

show abstract

“…Chemiluminescence represents the emanation of light in a chemical reaction in which a molecule is thermally activated and experiences a nonadiabatic transition to an electronic excited state of the fragmentation product. − The process is called bioluminescence when it occurs in living organisms, e.g., fireflies. Chemiluminescence or bioluminescence has wide-ranging applications, such as treating cancers via photodynamic therapy, − acting as a bioluminescence imaging tool, , and tracking environmental pollutants .…”

mentioning

confidence: 99%

Dissociation Time, Quantum Yield, and Dynamic Reaction Pathways in the Thermolysis of trans-3,4-Dimethyl-1,2-dioxetane

Zhou,

Shu,

Wang

et al. 2024

J. Phys. Chem. Lett.

View full text Add to dashboard Cite

The thermolysis of trans-3,4-dimethyl-1,2-dioxetane is studied by trajectory surface hopping. The significant difference between long and short dissociation times is rationalized by frustrated dissociations and the time spent in triplet states. If the C–C bond breaks through an excited state channel, then the trajectory passes over a ridge of the potential energy surface of that state. The calculated triplet quantum yields match the experimental results. The dissociation half-times and quantum yields follow the same ascending order as per the product states, justifying the conjecture that the longer dissociation time leads to a higher quantum yield, proposed in the context of the methylation effect. The populations of the molecular Coulomb Hamiltonian and diagonal states reach equilibrium, but the triplet populations with different S z components fluctuate indefinitely. Certain initial velocities, leading the trajectories to given product states, can be identified as the most characteristic features for sorting trajectories according to their product states.

show abstract

Constructing the Mechanism of Dinoflagellate Luciferin Bioluminescence Using Computation

Cited by 3 publications

References 68 publications

Mechanistic Investigation into Chemiluminescence from 1,4-Benzoquinone

Mechanistic Investigation into Chemiluminescence from 1,4-Benzoquinone

Chemiluminescence of a Firefly Luciferin Analogue Reveals that Formation of the Key Intermediate Responsible for Excited State Generation Occurs on a Fully Concerted Step

Dissociation Time, Quantum Yield, and Dynamic Reaction Pathways in the Thermolysis of trans-3,4-Dimethyl-1,2-dioxetane

Contact Info

Product

Resources

About