The Quantum Yield of the Chemiluminescence of Dimethylbiacridylium Nitrate and the Mechanism of Its Enzymically Induced Chemiluminescence*

Abstract

Quantum yields for dimethyibiacridyliuni ion chemiluminesceiice based 011 the amount of methyl acridone formed by treatment with either H,O, or with xanthine oxidasehypoxanthine in 0.01 M Na,CO, at pH 10.4 and at 25°C were found to lie between 0.01 I and 0.020 with an average of about 0.016. In mixed solvents containing pyridine and water or alcohol and water the emission spectrum of chemiluminescence of dimethylbiacridylium ions as well as those of diniethylbiacridene and its oxide were found to be identical with or very similar to the fluorescence of methyl acridone in the same solvent. A mechanism involving two successive two equivalent reductions of the diniethylbiacridylium ion to dimethylbiacridan followed by a radical attack and auto-oxidation leading to a compound which can undergo a reverse aldol type reaction to yield one (or two) molecule of methylacridone and one of a somewhat more reduced form is suggested. The kinetic equation relating maximum intensity of chemiluminescence tr) dimethylbiacridylium ion, hypoxanthine, xanthine oxidase, H+ and o2 concentrations was derived from the scheme suggested and found to fit satisfactorily the data obtained from a series of experiments in which the quantum yield was also obtained. INTRODUCTlONTHERE have been many studies on the chemiluminescence of dimethylbiacridylium ions (D") and related compounds and numerous iiivestigators have published spectra of the chemiluminescence as well as chemiluminescence and fluorescence spectra of certain related acridine derivatives.(** 149 15* 'O, ")SO far as can be determined none ofthe chemiluminescence spectra reported have been "correct" in the sense that they were free of appreciable self absorption or of fluorescence due to energy transfer to molecules not themselves involved in the chemiluminescence. The investigators were in nearly every case aware of this difficulty but instrumentation did not permit the use of sufficiently dilute solutions to obviate it.The availability of highly sensitive Iight measuring devices and of spectrofluorimeters equipped with sensitive photomultipliers made possible useful reinvestigations of the probable intermediates and end-products of 10, lO' dimethyl 9,9' biacridylium nitrate *

Adsorption of lucigenin on Ag nanoparticles studied by surface‐enhanced Raman spectroscopy: effect of different anions on the intensification of Raman spectra

“…The extent of aggregation induced on the Ag colloid of the above anions is compared in Fig. 3, showing an increase in aggregation in the order Cl > SO 4 2 > NO 3 . From this result we deduced a larger effect of the halide on the particle aggregation when Luc 2C is also present.…”

“…SERS spectra of Luc 2C(10 5 M) in Ag colloid at a 10 2 M concentration in the absence of anion (a) and after adding (b) SO4 2 , (c) NO3 , and (d) Cl (10 2 M in all cases). exc D 1064 nm, 400 mW.…”

Electrochemiluminescence of Acridines

“…It is used as a probe for superoxide anion in many applications due to its highly luminescent properties. Numerous studies of properties, reaction mechanisms and analytical applications of lucigenin have been carried out since its discovery. In recent years, lucigenin has emerged as an important ECL reagent.…”

Electrochemical Reduction of Lucigenin on Mercury in Aqueous Media

“…Voltammetric measurements were made by means of an i dO, -= -electronic system made up of an HQ Instruments 305 QM dt potentiostat, an HQ Instruments 105 wave generator, a Norland Prowler digital oscilloscope, and a Houston Instruments 2000 recorder. I-t curves were run with the aid -E°) -2130L -2YO] [1] = kSOL exp L RT of an EG&G PARC 273 potentiostat.…”