Studies on the Chemiluminescence of Luminol in Dimethylsulfoxide and Dimethylsulfoxide‐water Mixtures*

Abstract

Abstract— The absorption, fluorescence, and chemiluminescence (CL) characteristics of luminol have been studied in basic dimethylsulfoxide (DMSO) and various basic DMSO — water mixed solvents. It has been shown that the luminol dianion can be produced quantitatively in carefully deoxygenated ‘dry’ DMSO using potassium t‐butyl alcoholate (BTO) as the base. A direct correlation has been found between the intensity of CL and the concentration of luminol dianion, Indicating that the dianion is the reactive species in the chemiluminescent reaction in DMSO. Increasing concentrations of water in the mixed solvents greatly reduced the CL intensity because of the decrease in luminol dianion concentration. Solvent effects on the fluorescence of 3‐aminophthalic acid samples was noted and identified. Chemiluminescent spectra of luminol were run as a function of solvent composition, and compared with fluorescence spectra in the same media. The need for correcting these spectra for comparison was noted. Stopped flow kinetic studies were run in DMSO and DMSO‐water mixtures. These data can be interpreted on the basis of two second‐order steps and one first‐order step in the reaction. The first‐order step is probably last and probably arises from decomposition of a ‘peroxy’ intermediate. The rate constant for this step is k= 1·2±0·3×10‐1 sec‐1.

Use of an Artificial Miniaturized Enzyme in Hydrogen Peroxide Detection by Chemiluminescence

“…Horseradish peroxidase (HRP) catalyzes hydrogen peroxide activation and further oxidation of luminol, thus generating a moderately high and durable luminescence signal (LS). The mechanism of luminol oxidation by HRP has been studied in detail and involves several steps before light emission [ 37 , 39 , 40 , 41 , 42 , 43 , 44 ]. First, hydrogen peroxide induces the formation of the high oxidation state compound I (C-I) intermediate ( Scheme 1 ; step 1), which, in turn, oxidizes two equivalents of luminol, in the deprotonated form LH — under alkaline conditions, through the formation of the compound II (C-II) intermediate ( Scheme 1 ; steps 2–3).…”

Green Chemiluminescence of Highly Fluorescent Symmetrical Azo-Based Luminol Derivative

“…[5][6][7][8] Luminol derivatives with electron-releasing substituents show red shift with an enhancement of CL quantum yield. [9][10][11][12][13][14] and White et al, have synthesized alkyl derivatives of luminol to maximize the CL (λmax = 410 nm) quantum yield. 12 While substitution of amino or methoxy groups on luminol increases its CL intensity 13 , electron withdrawing substituents like chloro and nitro groups make it non fluorescent.…”

“…[9][10][11][12][13][14] and White et al, have synthesized alkyl derivatives of luminol to maximize the CL (λmax = 410 nm) quantum yield. 12 While substitution of amino or methoxy groups on luminol increases its CL intensity 13 , electron withdrawing substituents like chloro and nitro groups make it non fluorescent. [9][10][11][12][13][14] Zaitsu et al, have synthesized N-(4-substituted benzyl) isoluminol with substituents like, 4-bromo,4-methoxy and 4-nitro groups.The chemiluminescent intensities of these compounds were 0.03-4.7 times that of luminol.…”

“…12 While substitution of amino or methoxy groups on luminol increases its CL intensity 13 , electron withdrawing substituents like chloro and nitro groups make it non fluorescent. [9][10][11][12][13][14] Zaitsu et al, have synthesized N-(4-substituted benzyl) isoluminol with substituents like, 4-bromo,4-methoxy and 4-nitro groups.The chemiluminescent intensities of these compounds were 0.03-4.7 times that of luminol. 12 Naphthalene analogues of luminol have an extended aromaticity which leads to green chemiluminescence (λmax = 490 to 550nm).…”

Συνθεση Και Χημιφωταυγεια Ν-Μονο Και Νν-Δι-Ν-Αλκυλιωμενων Παραγωγων Της Ισολουμινολης

“…1.2.1ΑλκυλΙωση του 4-αμινο-Ν-μεθυλο-φθαλιμι81 ου,16, με π-τολου ολοσουλφονι κοϋς εστέρες.για μέν το 31 68%, ενώ για το 33α 23%, και το 33β 14% εως 39%.ηλεκτροαρνητικότητά της, η ενυδάτωση της, ο όγκος της, ο βαθμός διαχύσεως της και το φορτίο της επιδρούν στην αντίδραση.Ενας ιδανικός οργανικός διαλύτης για την κατάλυση δι επιφανείας πρέπει να είναι απρωτικός, έτσι ώστε να αποφεύγονται ισχυρές αλλη λεπιδράσεις μεταξύ των ζευγών των ανιόντων. Στην περίπτωση της καταλύσεως τύπου "υγρού-υγρού" πρέπει ο οργανικός διαλύτης να μην είναι αναμίζιμος με το νερό.…”