Mechanism of the Chemiluminescence of Lucigenin. II. The Charge-transfer Structure of Lucigenin and Reduction of 10,10′-Dimethyl-9,9′-biacridinium Dication by Electron Transfer from Nucleophiles

Abstract

Lucigenin (10,10′-dimethyl-9,9′-biacridinium dinitrate, DBA2+2NO3−) was found to be a CT complex between DBA2+ and NO3−. In the reaction of lucigenin with several nucleophiles in the absence of molecular oxygen or oxidizing agents the following four types of products were obtained, depending upon the relative power of the nucleophiles to donate electrons to DBA2+: (1) salts of DBA2+ (DBA2+2X−) which are the CT complex between DBA2+ and the nucleophiles, such as Cl−, Br−, SCN−, and I−, (2) the cation radical DBA\underset.+ produced by one-electron transfer from nucleophiles, such as C6H5COCH2− and CH3COCH2−, to DBA2+, (3) the biradical DBA\underset.2 produced by two-electron transfer from nucleophiles such as OH−, CN−, CCl3−, and C6H5S− and (4) 10,10′-dimethyl-9,9′-bi(dihydroacridinylidene) produced from DBA\underset.2. Only the nucleophiles of (3), which produced DBA\underset.2 brought about the luminescence of lucigenin in the presence of oxygen, and DBA\underset.2 also showed luminescence in organic solvents in the presence of oxygen. From these findings it was concluded that the first process of the chemiluminescent reaction of lucigenin was the electron transfer reduction of DBA2+ by the nucleophiles to form the biradical DBA\underset.2.

A new electrochemiluminescent sensing interface for clonazepam based on titanate nanotubes self-assembled film

“…It can be known from Fig. 2 that the main reason for generation of the ECL of lucigenin is due to the reaction between lucigenin and the electrogenerated oxygen radical [1,2]. Our preliminary experiments showed that clonazepam did not give ECL emission on the TNTs/chitosan film-modified electrode, while it could greatly enhance the ECL intensity of luciginin in KCl solution on the TNTs/chitosan film-modified electrode.…”

“…Thereby, it is becoming a powerful detection method in recent years. Lucigenin (N,Ndimethyl-9,9 -biacrid-inium dinitrate) is an important ECL reagent, and considerable studies with regard to its chemiluminescence (CL) mechanism have been published [1,2]. However, owing to its low sensitivity and easy electrode fouling, less attention has been paid to the ECL of lucigenin than to its chemiluminescent.…”

Multichannel electrogenerated chemiluminescence of lucigenin in neutral and alkaline aqueous solutions on a gold nanoparticle self-assembled gold electrode

“…A new ECL peak was found at À0.03 V in KI solution upon reversal of the potential scan from À1.6 V. As intensity of this ECL peak was too weak to measure its spectrum, it was impossible to explain the formation mechanism at this moment. The slight difference in ECL intensity in different electrolytes and the emergence of new ECL peak in KI solution were probably due to the formation of charge- transfer complex between lucigenin and halogen ions [5], which might have certain effect on the generation of intermediate.…”

“…The most important ECL reactions in the analytical and bioanalytical fields include luminol, ruthenium (II) tris (2,2 0 -bipyridine), and acridinium ester [2]. Lucigenin (N,N 0 -dimethyl-9,9 0 -biacridinium dinitrate) is one kind of acridinium ester and numerous studies [3][4][5][6] concerning the mechanism of lucigenin chemiluminescence (CL) have been carried out since it was reported in 1935 by Gleu and Petsch [7]. As ECL is advantageous over CL, the ECL and electrochemistry of lucigenin have already been investigated in aqueous and non-aqueous media at different electrodes [8][9][10][11][12] and the mechanism of ECL has also been discussed.…”

Flow Injection Determination of Ascorbic Acid by Iron(III)-Catalyzed Lucigenin Chemiluminescence in a Micellar System

“…The formation of charge-transfer (CT) complexes between the biacridinium cation and various anions was also investigated with respect to the lucigenin CL reaction. 18 Lucigenin is known to react with the reductants14, such as ascorbic acid, glucose, urea and iron(II), to form intense CL light over a wavelength range of 420 -510 nm in the same manner as an oxidant, such as hydrogen peroxide. 19 On the other hand, flow injection analysis (FIA) is one of the simplest approaches to the automation of chemical analysis, and is being applied to a wide variety of analytical fields.…”