Peroxyoxalate chemiluminescence enhanced by oligophenylenevinylene fluorophores in the presence of various surfactants

Article first published online: 15 JAN 2014The effect of several surfactants on peroxyoxalate chemiluminescence (PO-CL) using oligophenylenevinylene fluorophores was investigated. Among several oligophenylenevinylenes consisting of stilbene units, linearly conjugated ones, such as distyrylbenzene and distyrylstilbene, effectively enhanced PO-CL efficiency. Various effects of anionic, cationic, amphoteric and non-ionic surfactants on the CL efficiency of PO-CL were determined using three oxalates and the distyrylbenzene fluorophore. Anionic and non-ionic surfactants effectively enhanced CL efficiency, in contrast to the negative effect of cationic and amphoteric surfactants. Non-ionic surfactants were also effective in CL reactions of oxalates bearing dodecyl ester groups by the hydrophobic interaction between their alkyl chains. Considering these results, the surfactants not only increase the concentrations of water-insoluble interacting species in the hydrophobic micelle cores, but also control rapid degradation of the oxalates by alkaline hydrolysis. Copyright © 2014 John Wiley & Sons, Ltd.ArticleLUMINESCENCE. 29(7):772-778 (2014)journal articl

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

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 (σp+) of the DSBs and the singlet chemiexcitation yields (ΦS) 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.ArticleJournal of Photochemistry and Photobiology A: Chemistry. 252:222-231 (2013)journal articl

A new cyano-substituted fluorescamine superior to its original form as a fluorescent probe for amino acid detection

Available online 7 February 2018.Synthesis and spectral study of two new cyano-substituted fluorescamine as the fluorescent probes for amino acid detection have been carried out comparing with the original fluorescamine. Of the three compounds, the derivative with a cyano group at the meta-position on the 4-phenyl group was found to be superior to the original one in the reactivity toward some amino acids as well as the fluorescence intensity of the adducts. The fluorescent amino acid adducts were also applied to the peroxyoxalate chemiluminescence system as the fluorophores, in which the derivative described above was found to be more effective also in chemiluminescence than the original one. (C) 2018 Elsevier Ltd. All rights reserved.ArticleTETRAHEDRON LETTERS. 59(12):1104-1107 (2018)journal articl

Chemically-induced geometrical isomerization of stilbenes during peroxyoxalate chemiluminescence reaction: revisit to 'photochemistry without light'

The chemically-induced isomerization of stilbenes during the peroxyoxalate chemiluminescence (PO-CL) reactions was reinvestigated. The PO-CL reactions using bis(2,4,6-trichlorophenyl) oxalate in the presence of several stilbenes (type A reaction) produced cis-stilbenes in 0-4% yields, which was dependent on the singlet excitation energy of the stilbenes. On the other hand, the PO-CL reactions of the oxalates, containing the stilbene moieties in the molecules (type B reaction), produced cis-stilbenes 0-9.3% yields, some of which were much more effective than the type A reactions considering the amount of the oxalate moiety as the energy supplier.ArticleTETRAHEDRON LETTERS. 55(3):619-622 (2014)journal articl

Chemiluminescence behavior of fluorescent aromatics tethered 9-methylidene-10-methylacridans involving chemiluminescence resonance energy transfer (CRET) quenching

The chemiluminescence (CL) behavior, observed in the singlet oxygenation of three fluorescent aromatics tethered 9-methylidene-10-methylacridans bearing the pyrene, perylene, and stilbene moieties, was investigated. The CL spectrum of 9-(perylen-3′-ylidene)-10-methylacridan displayed a red-shifted emission different from the fluorescent products, while 9-(pyren-1′-ylidene)-10-methylacridan and 9-(4′-styrylbenzylidene)-10-methylacridan produced very weak CLs. A chemiluminescence resonance energy transfer (CRET) quenching of the excited aromatic aldehydes by the acridans remaining as the unreacted reactants was found to result in these unexpected CL behaviors.ArticleTetrahedron Letters. 54(11):1338-1343 (2013)journal articl

Control of peroxyoxalate chemiluminescence by nitrogen-containing ligand quenching: turning off and on by ligand-metal ion host-guest interactions

ArticleTETRAHEDRON. 67(36):6927-6933 (2011)journal articl

Fluorescence and chemiluminescence behavior of distyrylbenzene bearing two arms of dipicolylaminomethyl groups: Interactions with zinc ion and ATP

Available online 31 January 2018.The absorption and fluorescence spectral study of the distyrylbenzene bearing two arms of the dipicolylaminomethyl groups, the effective ligands for Zn2+, was studied in the presence of Zn2+ and ATP. Upon complexation of the distyrylbenzene with zinc ions in acetonitrile, enhancement of the fluorescence intensity was observed due to inhibition of intramolecular PET (photo-induced electron transfer) quenching, but no effect was found in aqueous media because the equilibrium laid to the free form of the ligands. In contrast, the addition of ATP disodium salt was effective to enhance the fluorescence intensity of the combination of the distyrylbenzne and Zn2+ in aqueous media. This assembly was applied to the peroxyoxalate chemiluminescence system and a significant increase in the intensity was observed, which provides a potential detection for ATP by chemiluminescence. (C) 2018 Elsevier B.V. All rights reserved.ArticleSPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY. 195:223-229 (2018)journal articl