Use of coumarin derivatives as activators in the peroxyoxalate system in organic and aqueous media
Graphical abstract
Introduction
Coumarin derivatives are widely distributed in the plant kingdom, some of them show physiological activity, whereas many derivatives are of great interest for diverse practical applications. [[1], [2], [3], [4], [5], [6], [7]] Synthetic coumarin derivatives are widely utilized as laser dyes [[8], [9], [10]], optical brighteners [11], as well as fluorescence labels [[12], [13], [14], [15]]. Additionally, some coumarin derivatives show antimicrobial properties and others are employed as fluorescence probes for the determination of proteolytic enzyme activity in biological fluids [16], in fluorescence immunoassays [17,18], for intercellular cerebral pH measurements [19], as well as in the treatment of skin diseases [[19], [20], [21]].
On the other hand, chemiluminescence systems have been utilized in a great variety of analytical and bioanalytical assays. [[22], [23], [24], [25], [26], [27], [28], [29], [30]] The general mechanisms of organic chemiluminescence involve the unimolecular decomposition of cyclic peroxides (1,2-dioxetanes or 1,2-dioxetanones) with the preferential generation of triplet-excited states [[31], [32], [33]] and a catalytic process, where peroxide decomposition is initiated by and electron or charge transfer from an appropriate catalyst, called activator (ACT) [34]. The catalyzed decomposition, denominated Chemically Initiated Electron Exchange luminescence (CIEEL,) can lead to the preferential formation of emissive singlet excited states, however, the efficiency of the intermolecular process is generally low, eventually due to sterical hindrance. [[35], [36], [37]] Contrarily, when the CIEEL process is of intramolecular nature, the efficiency is very high, being able to reach quantum yields of up to 1.0 E/mol [[38], [39], [40], [41]]. The most efficient intramolecular CIEEL system is the induced decomposition of 1,2-dioxetane derivatives containing a protected phenoxyl moiety as substituent, generating, upon deprotection with a chemical reagent or enzymatically, phenolate as an excellent internal electron donor [[42], [43], [44]]. This kind of 1,2-dioxetanes is the basis for a wide variety of chemiluminescent immunoassay and several other bioassays related to the determination of enzyme activities [[45], [46], [47], [48], [49]].
As outlined above, the singlet quantum yields and thereby chemiluminescence emission quantum yields in intermolecular CIEEL systems are generally low (in the order of 10−4 E/mol). [35,38] Contrarily, the peroxyoxalate reaction possesses very high efficiency [[50], [51], [52]], moreover the occurrence of an electron or charge transfer in its chemiexcitation step between a high-energy intermediate (HEI) formed and an activator (ACT) has been unequivocally shown [[52], [53], [54], [55]]. This highly efficient chemiluminescence reaction, with widespread analytic and practical applications [22,30,56,57], consists in the base-catalyzed reaction of activated oxalic acid derivatives with hydrogen peroxide in the presence of a highly fluorescent chemiluminescence ACT with low oxidation potential, leading to the formation of carbon dioxide and light emission form the ACT [50,58]. The reaction proceeds by base catalyzed hydrogen peroxide attack to the oxalate derivative with formation of a monoperoxalate derivative, [[59], [60], [61], [62]] which, upon cyclization, leads to the formation of a cyclic four-membered peroxide, most likely 1,2-dioxetanedione (Scheme 1). [55,[62], [63], [64]] The interaction of this HEI with the ACT, initiated by a charge or electron transfer from the ACT to the HEI, leads to peroxide cleavage and the ACT’s excited singlet state formation, resulting in chemiluminescence by fluorescence emission from the ACT (Scheme 1). [52,53] The use of ACTs with different fluorescence emission wavelengths leads to differently colored chemiluminescence emission [[65], [66], [67], [68], [69]].
Due to the facts that coumarin derivatives are widely utilized in bioassays in vitro and in vivo, as well as the peroxyoxalate reaction being highly efficient and adequate for the utilization in chemiluminescence assay, the peroxyoxalate chemiluminescence is studied here with three different representative coumarin derivatives as activators (COU120, COU151 and COU153), using the commercially available and widely utilized bis(2,4,6-trichlorophenyl) oxalate (TCPO), as well as the new, non-toxic bis(3-(methoxycarbonyl)phenyl) oxalate (MCPO) derivative, in anhydrous as well as aqueous media.
Section snippets
Experimental section
Bis(2,4,6-trichlorophenyl) oxalate (TCPO) (Sigma ≥ 99 %) was recrystallized from a chloroform/n-hexane mixture (14:5) (mp 189 - 191 °C, lit. 190 °C). [70] Imidazole (IMI-H, Sigma, 99 %), coumarins 153, 151 and 120 (all Aldrich) were used without further purification.
Bis(3-(methoxycarbonyl)phenyl) oxalate (MCPO) was synthesized from the reaction between methyl 3-hydroxybenzoate and oxalyl chloride following the procedure previously reported for methyl salicylate as phenol derivative. [71] Methyl
Results and discussion
The imidazole catalyzed reactions of the oxalates TCPO and MCPO with hydrogen peroxide in DME and DME / water in the presence of the three activators COU121, COU151 and COU153 were studied in standard conditions ([TCPO] =0.10 mmol L−1 or [MCPO] =0.10 mmol L−1; [IMI-H] =2.0 mmol L−1, 5.0 mmol L−1 or 10 mmol L−1; [H2O2] = 10 mmol L−1), leading to kinetic emission curves easily observed in a conventional fluorimeter. The reactions are considerably faster in the aqueous medium as compared to pure
Conclusions
Coumarins, like the derivatives COU120, COU151 and COU153 can be utilized as activators in peroxyoxalate chemiluminescence in anhydrous and aqueous media, leading to reproducible results. Singlet quantum yields are similar to that obtained with the commonly utilized polycondensed aromatic hydrocarbon activators. The environmentally compatible oxalic ester bis(3-(methoxycarbonyl)phenyl) oxalate (MCPO) leads to slightly lower quantum yields than the commonly utilized polychlorinated derivative
CRediT authorship contribution statement
Maidileyvis C. Cabello: Investigation, Writing - original draft, Formal analysis, Visualization. Liena V. Bello: Investigation, Formal analysis, Visualization. Wilhelm J. Baader: Conceptualization, Writing - original draft, Writing - review & editing, Project administration, Funding acquisition.
Declaration of Competing Interest
The authors report no declarations of interest.
Acknowledgements
The authors would like to thank Solvay Peróxidos do Brasil for a generous donation of hydrogen peroxide. The authors also would like to thank funding by Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq), Brazil (MCC (147138/2016-7), LVB (141816/2017-1)) for financial support in the form of PhD fellowships and Coordenadoria de Aperfeioamneto de Pessoal de Ensino Superior (CAPES), Brazil, for support to the Graduate Progaram of Chemistry, IQUSP. Furthermore, the generous
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