Effect of ionic liquids on the kinetics and quantum efficiency of peroxyoxalate chemiluminescence in aqueous media

Cabello, Maidileyvis Castro; Seoud, Omar A. El; Baader, W. J.

doi:10.1016/j.jphotochem.2018.08.012

Cited by 14 publications

(31 citation statements)

References 65 publications

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“…This is in agreement with results obtained before for the reaction in anhydrous conditions (4,5,(15)(16)(17). The singlet quantum yield at infinite activator concentration of Ф S ∞ = (5.8 AE 0.2) × 10 -7 E mol -1 is significantly lower than yields commonly determined in anhydrous media (3,16,17,32) however, comparable to quantum yields observed in partially aqueous media (25,26,42). The perhydrolysis and the hydrolysis pathway, which lead to light emission and dark TCPO decomposition, respectively, have the same bimolecular rate constants (Table 1 and Scheme 3).…”

Section: Hcosupporting

confidence: 92%

“…This is in agreement with results obtained before for the reaction in anhydrous conditions (4,5,15–17). The singlet quantum yield at infinite activator concentration of Ф S ∞ = (5.8 ± 0.2) × 10 –7 E mol –1 is significantly lower than yields commonly determined in anhydrous media (3,16,17,32) however, comparable to quantum yields observed in partially aqueous media (25,26,42).…”

Section: Discussioncontrasting

confidence: 54%

“…These low quantum yields should be caused by a lower efficiency of the chemiexcitation step of the peroxyoxalate reaction in aqueous media (1)(2)(3). This situation has been observed before for other peroxyoxalate reaction systems (24)(25)(26)42), as well as other chemiluminescence reactions (1-3); however, no general explanation could be given up to date.…”

Section: Hcomentioning

confidence: 85%

“…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%

“…Although the peroxyoxalate reaction mechanism has been studied mainly in anhydrous media, our group has shown recently that this reaction is viable in aqueous media, using lutidine, borate, salicylate and phosphate catalysts (24)(25)(26)42) Both specific base catalysis, in the case of salicylate, and general base catalysis, in the case of lutidine and phosphate, have been observed, without a clear way to predict which one will happen in a given condition (i.e., solvent type, nature of the base).…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Hcosupporting

confidence: 92%

Section: Discussioncontrasting

confidence: 54%

Section: Hcomentioning

confidence: 85%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Mechanistic Study of the Peroxyoxalate System in Completely Aqueous Carbonate Buffer

Augusto

Bartoloni

Pagano

et al. 2020

Photochem & Photobiology

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Vorbeugen oder Heilen – die beispiellose Notwendigkeit von selbstberichtenden Materialien

2021

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Hatice Mutlu, geboren in Bulgarien, studierte Chemie an der Marmara Universitätu nd der Bogazici Universität. Anschließend promovierte sie am KIT in der Gruppe von M. A. R. Meier.Nach Postdoc-Aufenthalten in den Gruppen von J.-F. Lutz (ICS-CNRS, Straßburg) und C. Barner-Kowollik (KIT) arbeitet sie derzeit als leitende Wissenschaftlerin am KIT.I hr Forschungsinteresse reicht von der Synthese komplexer makromolekularer Architekturen und funktioneller Polymere bis hin zur Entwicklung neuer polymerbildender Reaktionen und neuartiger Konjugationschemien mit besonderem Schwerpunkta uf dem Design neuartiger schwefelbasierter und selbstberichtender Materialien. Christopher Barner-Kowollik schloss sein Chemistudium an der UniversitätG çttingen ab. Anfang 2000 ging er an die Universität New South Wales und übernahmdort 2006 als einer der Direktoren die Leitung des Centre for Advanced Macromolecular Design. 2008 kehrte er nach Deutschland an das KIT zurück, wo er einen DFG-gefçrderten SFB zu Synthese und Struktur weicher Materie aufbaute und leitete. 2017 wechselte er zur QUT und baute das QUT-Laborf ür weiche Materialwissenschaften auf. Seine Forschungsleistungen wurden durch eine Reihe von nationalen und internationalen Preisen anerkannt.

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Prevent or Cure—The Unprecedented Need for Self‐Reporting Materials

2021

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Hatice Mutlu, born in Bulgaria, studied Chemistry at Marmara University and Bogazici University.S ubsequently, she obtained her PhD from the Karlsruhe Institute of Technology (KIT) in the group of M. A. R. Meier.After post-doctoral stays in the groups of J.-F. Lutz (ICS-CNRS, Strasbourg) and C. Barner-Kowollik (KIT), she currently works as asenior researcher at KIT.Her research interest spans from the synthesis of complex macromolecular architecturesand functional polymers to the development of new polymer-forming reactions and novel conjugation chemistries with aparticularfocus on the design of novel sulfur-based and self-reporting materials. Christopher Barner-Kowollik, Australian Research Council (ARC) Laureate Fellow, graduated in chemistry from Gçttingen University,G ermany,and joined the University of New South Wales in early 2000 rising to lead the Centre for Advanced Macromolecular Design in 2006 as one of its directors. He returned to Germany to the KIT in 2008, where he establishedand led aDFG-funded Centre of Excellence in soft matter synthesis. He moved to QUT in 2017 and established QUT'sSoft Matter Materials Laboratory. His research achievements have been recognized by an array of national and international awards.

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Effect of ionic liquids on the kinetics and quantum efficiency of peroxyoxalate chemiluminescence in aqueous media

Cited by 14 publications

References 65 publications

Mechanistic Study of the Peroxyoxalate System in Completely Aqueous Carbonate Buffer

Mechanistic Study of the Peroxyoxalate System in Completely Aqueous Carbonate Buffer

Vorbeugen oder Heilen – die beispiellose Notwendigkeit von selbstberichtenden Materialien

Prevent or Cure—The Unprecedented Need for Self‐Reporting Materials

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