A simplified model for the dynamics of chemiluminescence in the oxalate-hydrogen peroxide system: toward a reaction mechanism

Orlović, Mirko; Schowen, Richard L.; Givens, Richard S.; Álvarez, Francisco J.; Matuszewski, B.K.; Parekh, Nikhil J.

doi:10.1021/jo00276a021

Cited by 90 publications

(52 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…5a and well fitted by the single exponential decay as shown in Fig. 5b as has been observed for the typical PO-CL [12,13,45]. The pseudo-first-order decay rate constants (k) estimated from the logarithmic plots of the decay curves (Fig.…”

Section: Dsb Enhanced Po-cl Reactions Of the Eight Oxalates And The Hsupporting

confidence: 73%

The Hammett correlation between distyrylbenzene substituents and chemiluminescence efficiency providing various ρ-values for peroxyoxalate chemiluminescence of several oxalates

Maruyama

Narita

Motoyoshiya

2013

Journal of Photochemistry and Photobiology A: Chemistry

View full text Add to dashboard Cite

Peroxyoxalate chemiluminescence (PO-CL) was investigated using eight oxalates with various phenol moieties and the distyrylbenzene (DSB) fluorophores with various substituents. The ρ-values in the Hammett correlation between the substituent constants (σ p + ) of the DSBs and the singlet chemiexcitation yields (Φ S ) for the PO-CL reactions varied from -0.50 to -1.01 depending on the oxalate structure, and the reactive oxalates tended to afford the higher absolute ρ-values but with a few exceptions. Based on the CIEEL mechanism, these experimental observations suggest that the aryloxy groups still remain in the 1,2-dioxetanones (DOTs), which are the postulated high-energy intermediates, and control the electronic properties of DOTs as electron-acceptors. The LUMO energies of the DOTs calculated by the ab initio method with a B3LYP/6-31g(d) basis set reveal that the lower the DOT-LUMO energies, the higher the absolute ρ-values were provided for the corresponding oxalates, as predicted by the frontier molecular orbital (FMO) theory. Thus, the chemical species interacting with the DSBs would be not unitary and will be DOTs.2

show abstract

Section: Dsb Enhanced Po-cl Reactions Of the Eight Oxalates And The Hsupporting

confidence: 73%

The Hammett correlation between distyrylbenzene substituents and chemiluminescence efficiency providing various ρ-values for peroxyoxalate chemiluminescence of several oxalates

Maruyama

Narita

Motoyoshiya

2013

Journal of Photochemistry and Photobiology A: Chemistry

View full text Add to dashboard Cite

show abstract

“…Mechanism for the peroxyoxalate chemiluminescence of TCPO with imidazole (IMI-H) as catalyst, as proposed by Orlovic et al 35 Thereafter, Milofsky and Birks published another article about a mechanistic study on the PICL with the PO reaction, taking advantage of the fact that they excluded the necessity to add hydrogen peroxide to initiate the PO reaction, which could simplify the kinetic expression for the light emission. 39 The authors studied this system in several experimental conditions, and were able to propose a reaction mechanism, including several speculative high-energy intermediate structures (see below).…”

Section: Methodsmentioning

confidence: 99%

“…Mechanistic pathway for HEI formation in the peroxyoxalate system, as proposed by Alvarez et al 34 In a subsequent study, Orlovic and coworkers 35 used imidazole as catalyst for the PO reaction which was shown in a previous work to be a better catalyst than triethylamine. 36 The kinetic behavior of the system in aqueous acetonitrile was significantly more complicated than in anhydrous media, demanding a much more complex set of kinetic expressions to be simulated.…”

mentioning

confidence: 97%

The chemiluminescent peroxyoxalate system: state of the art almost 50 years from its discovery

Francisco¹,

Ciscato²,

Augusto³

et al. 2012

Arkivoc

View full text Add to dashboard Cite

Almost fifty years after the discovery of the peroxyoxalate reaction by E. A. Chandross in the early nineteen sixties, this review article intends to give a general overview on mechanistic aspects of this system and to describe the principles of its analytical application. After a short general introduction on the principles of chemiluminescence and the history of peroxyoxalate discovery, mechanistic aspects of high-energy intermediate formation, its structure and its reaction with an activator in the peroxyoxalate system are discussed. Finally, analytical applications of peroxyoxalate chemiluminescence are exemplified using representative recent examples, including oxalic acid detection in biological samples.

show abstract

“…In order to evaluate the kinetic data for the PO-CL system studied from the resulting CL intensity-time plots, a pooled intermediate model was used. 32,38 According to this model, the CL reaction is simplified as:…”

Section: Kinetic and Possible Mechanismmentioning

confidence: 99%

Indirect Chemiluminescence-based Determination of Catecholamines in Pharmaceutical Formulations by Furandicarboxylate Derivative as a Novel Blue Fluorescer in Peroxyoxalate-H2O2 System

et al. 2013

View full text Add to dashboard Cite

A novel, simple, cheap, and high sensitivity batch chemiluminescent method for the determination of catecholamine drugs, epinephrine (E), dopamine (DA) and methyldopa (MD) at microgram levels in pharmaceutical formulations is described. The method is based on a chemiluminescence (CL) system arising from the reaction of bis(2,4,6-trichlorophenyl) oxalate (TCPO) with H2O2 in the presence of a novel fluorescer, furandicarboxylate, and is proposed as a new analytical method for the determination of catecholamines. The method is based on the inhibition of CL emission by DA and its enhancement by E and MD. Under optimal conditions, good linear ranges were obtained, 0.5 -12.7, 0.06 -1.83 and 0.069 -3.52 μg/mL with detection limits of 0.30, 0.03 and 0.04 μg/mL (S/N = 3) for DA, E and MD, respectively. Moreover, a pooled-intermediate model was used to determine the kinetic parameters of CL with and without catecholamines and a possible CL mechanism was discussed.

show abstract

A simplified model for the dynamics of chemiluminescence in the oxalate-hydrogen peroxide system: toward a reaction mechanism

Cited by 90 publications

References 0 publications

The Hammett correlation between distyrylbenzene substituents and chemiluminescence efficiency providing various ρ-values for peroxyoxalate chemiluminescence of several oxalates

The Hammett correlation between distyrylbenzene substituents and chemiluminescence efficiency providing various ρ-values for peroxyoxalate chemiluminescence of several oxalates

The chemiluminescent peroxyoxalate system: state of the art almost 50 years from its discovery

Indirect Chemiluminescence-based Determination of Catecholamines in Pharmaceutical Formulations by Furandicarboxylate Derivative as a Novel Blue Fluorescer in Peroxyoxalate-H2O2 System

Contact Info

Product

Resources

About