Study of coelenterazine luminescence: Electrostatic interactions as the controlling factor for efficient chemiexcitation

Magalhães, Carla M.; Silva, Joaquim C. G. Esteves da; Silva, Luís Pinto da

doi:10.1016/j.jlumin.2018.03.069

Cited by 23 publications

(93 citation statements)

References 66 publications

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“…By determining energy and kinetic chemiluminescent profiles, we have found that chemiluminescence has a higher reaction rate at higher pH, whereas it presents stronger light emission with decreasing pH. Despite this, these differences cannot be explained by considering different emitters . Subsequent density functional theory (DFT) and time‐dependent (TD)‐DFT calculations allowed us to explain these findings by taking into account the ionization state of the dioxetanone intermediate .…”

Section: Introductionmentioning

confidence: 84%

“…We found that despite both molecules undergoing different chemiexcitation pathways, both dioxetanone species decompose with significant ET/BET and CT/BCT between the imidazopyrazinone and dioxetanone moieties . Furthermore, other neutral dioxetanones allowed for efficient chemiexcitation, but their thermolysis occurred without significant ET/CT . Thus, neither ET/BET nor CT/BCT has any clear relationship with efficient chemiexcitation.…”

Section: Introductionmentioning

confidence: 95%

“…More recently, our group performed combined experimental and theoretical studies regarding the chemiluminescence of Cypridina luciferin and Coelenterazine . By determining energy and kinetic chemiluminescent profiles, we have found that chemiluminescence has a higher reaction rate at higher pH, whereas it presents stronger light emission with decreasing pH.…”

Section: Introductionmentioning

confidence: 97%

“…Moreover, the S 0 →S 1 energy gap within the biradical region for ionic peroxides is significantly higher than for neutral dioxetanones, which indicates a lower efficiency of chemiexcitation . These conclusions have been supported by experimental studies on imidazopyrazinones and other systems . Indirect experimental data obtained from both Cypridina and the firefly systems also indicate that efficient chemiexcitation is caused by the thermolysis of neutral dioxetanones .…”

Section: Introductionmentioning

confidence: 99%

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Mechanistic insights into the efficient intramolecular chemiexcitation of dioxetanones from TD‐DFT and multireference calculations

Silva

Magalhães

2018

Int J of Quantum Chemistry

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Despite decades of research, it is still not clear what is the mechanism behind the efficient chemiexcitation of dioxetanones in chemiluminescent and bioluminescent reactions. In fact, long‐standing theories (charge transfer‐initiated luminescence and chemically induced electron‐exchange luminescence) have been demonstrated to not be able to explain this phenomenon. Herein, a theoretical approach using reliable and up‐to‐date methodology was used to address this problem, by focusing on model dioxetanones. Time‐dependent (TD)‐Density functional theory (DFT) and multireference complete‐active‐space second‐order perturbation theory (CASPT2) calculations provided evidence that points to efficient intramolecular chemiexcitation being the result of the reacting molecules having access to a long zone of the Potential energy surface (PES), within the biradicalar region, where S0 and S1 are degenerate. Molecules with inefficient chemiexcitation are unable to reach this zone of degeneracy. Our main finding is that access to the region of degeneracy appears to be given due to increased interaction between the keto and CO2 moieties, as supported by the use of the activation strain model and Born‐Oppenheimer molecular dynamics, which extends the biradical region by delaying the rupture of the peroxide ring. Increased interaction derives from attractive electrostatic interactions between the moieties of dioxetanone. Thus, we hypothesize that efficient chemiexcitation results not only from electron/charge transfer and subsequent charge annihilation but is instead based on the degree of interaction between the keto and CO2 moieties, which controls the access to a region of degeneracy between the ground and excited states.

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Section: Introductionmentioning

confidence: 84%

Section: Introductionmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

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Mechanistic insights into the efficient intramolecular chemiexcitation of dioxetanones from TD‐DFT and multireference calculations

Silva

Magalhães

2018

Int J of Quantum Chemistry

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“…As we known, the most widely applied substrates which can reaction with molecular oxygen are firefly luciferin and coelenterazine, unfortunately, firefly luciferin requires the addition of magnesium ion and ATP to trigger light emission, the process leading the light emission of coelenterazine requires the presence of calcium ion as co‐factors, which potentially leads to complex protocols in bioanalysis. For this reason, the co‐factors independent cypridina bioluminescence has attracted considerable attention from biologists and chemists.…”

Section: Introductionmentioning

confidence: 99%

The Fluorescent Properties of pH‐Independent Cypridina Oxyluciferin Derivatives

et al. 2019

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The co‐factors independent cypridina bioluminescence was often used to detect molecular oxygen. Whereas the native cypridina oxyluciferin and the majority analogues only emit blue light, it limits the application of the cypridina oxyluciferin derivative in detection active oxygen species. To overcome these limitations, we design two series of oxyluciferin derivatives: 2‐acetamido‐5‐aryl‐3‐(p‐trifluoromethylphenyl)pyrazine and 2‐acetamido‐5‐aryl‐3‐(p‐methoxylphenyl)pyrazine. The results found that the fluorescence emissions of the cypridina oxyluciferin derivatives cover the whole region of visible light. Especially, 2‐acetamido‐5‐(trans‐2,3,6,7‐tetrahydro‐1H,5H‐benzo[i,j]quinolizine‐ethenyl)‐3‐(p‐trifluoromethyl phenyl)pyrazine (1 h) can emit red light. By comparison of the emission spectra and oscillator strengths, it found that electron‐donating group in C3 position contributed to blue shift wavelength and improve luminous efficiency. The increasing conjugated length by introducing a conjugated double bond made the emission spectra shift to red and the luminescence strengths much stronger. Moreover, the analysis of the relative stabilities at the ground and excited states indicates that neutral forms, not amide ions, are dominant at physiological pH.

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Single-molecule chemiluminescent photosensitizer for a self-activating and tumor-selective photodynamic therapy of cancer

Silva

Núñez-Montenegro

Magalhães

et al. 2019

European Journal of Medicinal Chemistry

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Study of coelenterazine luminescence: Electrostatic interactions as the controlling factor for efficient chemiexcitation

Cited by 23 publications

References 66 publications

Mechanistic insights into the efficient intramolecular chemiexcitation of dioxetanones from TD‐DFT and multireference calculations

Mechanistic insights into the efficient intramolecular chemiexcitation of dioxetanones from TD‐DFT and multireference calculations

The Fluorescent Properties of pH‐Independent Cypridina Oxyluciferin Derivatives

Single-molecule chemiluminescent photosensitizer for a self-activating and tumor-selective photodynamic therapy of cancer

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