Peroxyoxalate chemiluminescence efficiency in polar medium is moderately enhanced by solvent viscosity

Souza, Sérgio Pereira de; Khalid, Muhammad; Augusto, Felipe A.; Baader, W. J.

doi:10.1016/j.jphotochem.2016.02.001

Cited by 20 publications

(13 citation statements)

References 62 publications

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“…The solvent effect might be a general medium polarity effect or a specific molecular water effect on the stabilization of radical ion pairs formed during the CIEEL sequence. The observed increase is surprising in a first instance, as it is known that the emission quantum yields of chemiluminescence transformations are generally much lower in aqueous media, as compared to anhydrous conditions (2,3,6,7,22,24–27,29). Therefore, this intriguing observation made in this work will be further investigated using photophysical approaches to rationalize the chemiexcitation quantum yields in the peroxyoxalate reaction of TCPO and DNPO in DME:H 2 O mixtures, in the conditions well established in the present work.…”

Section: Discussionmentioning

confidence: 95%

“…Kinetic studies, designed to distinguish between nucleophilic, specific base, and general base catalysis, in the reaction of TCPO with H 2 O 2 using 2,6‐lutidine (2,6‐dimethylpyridine) as catalyst, indicated the role of 2,6‐lutidine as general basic catalyst in both organic and aqueous medium (24). All these studies, performed in aqueous organic mixtures or entirely aqueous medium, revealed that the chemiluminescence emission efficiency of the peroxyoxalate reaction decreases drastically in aqueous media, as compared to anhydrous organic medium (6,7,22,26–29).…”

Section: Introductionmentioning

confidence: 99%

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Water Effect on Peroxyoxalate Kinetics and Mechanism for Oxalic Esters with Distinct Reactivities

Cabello

Baader

2021

Photochem & Photobiology

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The peroxyoxalate reaction is being widely used for various analytical and bioanalytical applications, and however, few mechanistic studies are performed in aqueous media, important mainly for bioanalytical applications, where low chemiluminescence emission quantum yields are obtained. In this sense, we report here kinetic studies on the peroxyoxalate reaction, using two commercially available and widely utilized esters, bis(2,4‐dinitrophenyl) oxalate (DNPO) and bis(2,4,6‐trichlorophenyl) oxalate (TCPO), in 1,2‐dimethoxyethane:water mixtures. The reaction of the much more reactive DNPO, in anhydrous and aqueous media, occurs by a direct nucleophilic attack of H2O2 to the oxalic ester, not involving nucleophilic catalysis by imidazole. Contrary, in the reaction of the less reactive TCPO with H2O2, imidazole acts mainly as nucleophilic catalyst. For both esters, experimental conditions are established where precise kinetic data and emission quantum yields can be obtained. Interestingly, the quantum yields in 1,2‐dimethoxyethane water mixtures increase up to a water concentration of 0.7 mol L–1 and decrease significantly with higher concentrations.

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Section: Discussionmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 99%

Water Effect on Peroxyoxalate Kinetics and Mechanism for Oxalic Esters with Distinct Reactivities

Cabello

Baader

2021

Photochem & Photobiology

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“…When gradually changing the solvent from pure toluene to 90 % DPM, and thus increasing the viscosity by a factor of 4.6, the CL quantum yields of two different dioxetane systems increased by a factor of 2.2 and 2.6, respectively, whereas the quantum yield of the PO‐CL increased by a factor of 9.4 . In more polar solvents, however, the effect of solvent viscosity on the CL was less pronounced as a 34‐fold increase in viscosity from pure ethyl acetate to pure dimethylphthalate only resulted in an increase in quantum yields of a factor of five for the PO‐CL . The presented viscosity dependency of both CL systems provides evidence for a rather stable complex within a solvent cage that facilitates EBT before the species can diffuse away.…”

Section: Mechanistic Insightsmentioning

confidence: 99%

All Eyes on Visible‐Light Peroxyoxalate Chemiluminescence Read‐Out Systems

Delafresnaye

Bloesser

Kockler

et al. 2019

Chemistry A European J

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Chemiluminescence (CL) reactions have been widely employed and explored over the past 50 years because they offer unique light emission upon a defined chemical stimulus. In this Minireview, we focus on peroxyoxalate (PO) compounds because they feature very high quantum yields tuneable over the entire visible spectrum, allowing for visible‐light detection by the naked eye without the necessity for expensive analytical instruments. Although analytical methods have been extensively described, PO‐CL read‐out is a strongly emerging field with ample industrial potential. The state‐of‐the‐art PO‐CL detection read‐out systems for various key analytes is here explored. In particular, structural requirements, recent developments of PO‐CL read‐out probes and current limitations of selected examples are detailed. Furthermore, innovative approaches and synthetic routes to push the boundaries of PO‐CL reactions into biological systems are highlighted. Underpinned by recent contributions, we share perspectives on embedding PO‐CL molecules into polymeric materials, which they consider the next step in designing high performance solid‐phase read‐out systems.

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“…In a recent analytical application, peroxyoxalate nanoparticles have been used in vivo for drug delivery and for imaging of hydrogen peroxide and glucose (18)(19)(20)(21)(22)(23). However, the mechanism leading to light emission in water is not as well characterized as in organic solvents, although the mechanism of the peroxyoxalate reaction has been studied in different media recently (24)(25)(26)(27)(28)(29)(30)(31).…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Study of the Peroxyoxalate System in Completely Aqueous Carbonate Buffer

Augusto

Bartoloni

Pagano

et al. 2020

Photochem & Photobiology

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The peroxyoxalate reaction is one of the most efficient chemiluminescence transformations, with emission quantum yields of up to 50%; additionally, it is widely utilized in analytical and bioanalytical assays. Although the real reason for its extremely high efficiency is still not yet understood, the mechanism of this transformation has been well elucidated in anhydrous medium. Contrarily, only few mechanistic studies have been performed in aqueous media, which would be of great importance for its application in biological systems. We report here our experimental results of the peroxyoxalate reaction in completely aqueous carbonate buffer, using fluorescein as chemiluminescence activator. The kinetics are very fast in the used basic conditions (pH > 9); despite this, reproducible kinetic results were obtained. The reaction proceeds by specific base catalysis, with rate‐limiting attack of hydrogen peroxide anion to the oxalic ester, in competition with ester hydrolysis by hydroxide ion. Emission quantum yields increase with the hydrogen peroxide concentration up to an optimal concentration of 10 mmol L–1. The infinite singlet quantum yield of (5.8 ± 0.2) × 10–7 is much lower than in anhydrous medium; however, it is similar to quantum yields measured before in partially aqueous media.

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Peroxyoxalate chemiluminescence efficiency in polar medium is moderately enhanced by solvent viscosity

Cited by 20 publications

References 62 publications

Water Effect on Peroxyoxalate Kinetics and Mechanism for Oxalic Esters with Distinct Reactivities

Water Effect on Peroxyoxalate Kinetics and Mechanism for Oxalic Esters with Distinct Reactivities

All Eyes on Visible‐Light Peroxyoxalate Chemiluminescence Read‐Out Systems

Mechanistic Study of the Peroxyoxalate System in Completely Aqueous Carbonate Buffer

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