Oxidative chemiluminescence

A remarkable number of organic compounds luminesce when subjected to consecutive oxidation-reduction (or reduction-oxidation) in aprotic solvents1-17 under conditions where anion radicals are oxidized or cation radicals are reduced. In many instances, the emission is identical with that of the normal solution fluorescence of the compound employed. In these instances the redox process has served to produce neutral molecules in an excited electronic state. These consecutive processes which result in emission are not special examples of oxidative chemiluminescence, but are more properly classified as electron transfer luminescence in solution since the sequence oxidation-reduction can be as effective as reduction-oxidation.8,10,12 A simple molecular orbital diagram, although it is a zeroth-order approximation of what might be involved under some conditions, provides a useful starting... 

Inhibitors reduce oxidative chemiluminescence by reducing the rate of light-producing peroxyl self-terminations (Scheme 1), by quenching electronically excited states (9) or simply by absorption of emitted light. The second factor may be much less important in polymers because of lowered rates diffusion (10). The rate of diffusion of 2,4-dihydroxybenzophenone in polypropylene has been... 

Following Ashby s first observation (7) of chemiluminescence from the oxidative degradation of polymers, a number of papers have appeared dealing with oxidative chemiluminescence from a variety of polymers (8-16). In this chapter we continue the 1,4-polyisoprene work with a study of the low-temperature chemiluminescence emitted in the autoxidation of three additional elastomers, cis-1,4-polybutadiene, amorphous 1,2-polybutadiene, and fmns-polypentenamer. We also report the chemiluminescence obtained from singlet-oxygenated samples of cis-1,4-polybutadiene and trans-polypentenamer, as well as rate data for singlet oxygen reactions with the 1,4-polyisoprene, 1,4-polybutadiene, and model compounds in solution. 

This chemiluminescence can be used to detect the presence of excess oxidant after a reductant has been oxidized. Chemiluminescent light levels are low, and darkened ambient conditions are needed to detect the chemiluminescence. 

CL has been used extensively to study the kinetics of polyamide oxidation. Chemiluminescence cannot be used to describe the oxidation rate of polyamides [619]. CL should be used only to evaluate the oxidation states of polyamides. Forsstrom... 

Camacho and Karlsson [35] investigated the thermal and thermo-oxidative stability of recycled PP, HDPE and a 20 80 PP/HDPE blend. These samples were subject to extrusion cycles. The oxidation induction time of all three samples decreased with the number of extrusion cycles, as did the temperature of oxidation. Chemiluminescence runs showed two peaks one sharp peak (corresponding to PP) and the other bimodal in shape (corresponding to PE). 

The value of electron donation in any oxidative chemiluminescence is seen in the chemiluminescence of (12) under autoxidative conditions. The quantum yield is higher than well known bright compounds such as luminol, 0 being 4.6% ... 

Again, linking these two groups via a methylene group as in (22) led to a compound which on oxidation chemiluminesced with an efficiency of 26% of that of luminol (ca. 3,3 x 1(T ). The chemiluminescence spectrum of (22), taken from the aqueous system, exhibits the bands of DP A fluorescence and also of naph-thalene-2,3-dicarboxylate. The latter is not represented in the chemiluminescence spectrum in the aprotic system, probably due to the fact that naphthalene-2,3-dicarboxylate fluorescence in DMSO is very weak [38]. 

Antioxidants have been shown to improve oxidative stabiHty substantially (36,37). The use of mbber-bound stabilizers to permit concentration of the additive in the mbber phase has been reported (38—40). The partitioning behavior of various conventional stabilizers between the mbber and thermoplastic phases in model ABS systems has been described and shown to correlate with solubiHty parameter values (41). Pigments can adversely affect oxidative stabiHty (32). Test methods for assessing thermal oxidative stabiHty include oxygen absorption (31,32,42), thermal analysis (43,44), oven aging (34,45,46), and chemiluminescence (47,48). 

Chemiluminescent Immunoassay. Chemiluminescence is the emission of visible light resulting from a chemical reaction. The majority of such reactions are oxidations, using oxygen or peroxides, and among the first chemicals studied for chemiluminescence were luminol (5-amino-2,3-dihydro-l,4-phthalazinedione [521-31-3]) and its derivatives (see Luminescent materials, chemiluminescence). Luminol or isoluminol can be directly linked to antibodies and used in a system with peroxidase to detect specific antigens. One of the first appHcations of this approach was for the detection of biotin (31). 

In the most common method for chemiluminescent immunoassay (GLIA), after the immunological reaction and any necessary separation steps, the labeled compounds or complexes react with an oxidizer, eg, hydrogen peroxide, and an enzyme, eg, peroxidase, or a chelating agent such as hemin or metal... 

Subsequent studies (63,64) suggested that the nature of the chemical activation process was a one-electron oxidation of the fluorescer by (27) followed by decomposition of the dioxetanedione radical anion to a carbon dioxide radical anion. Back electron transfer to the radical cation of the fluorescer produced the excited state which emitted the luminescence characteristic of the fluorescent state of the emitter. The chemical activation mechanism was patterned after the CIEEL mechanism proposed for dioxetanones and dioxetanes discussed earher (65). Additional support for the CIEEL mechanism, was furnished by demonstration (66) that a linear correlation existed between the singlet excitation energy of the fluorescer and the chemiluminescence intensity which had been shown earher with dimethyl dioxetanone (67). 

The first detailed investigation of the reaction kinetics was reported in 1984 (68). The reaction of bis(pentachlorophenyl) oxalate [1173-75-7] (PCPO) and hydrogen peroxide cataly2ed by sodium saUcylate in chlorobenzene produced chemiluminescence from diphenylamine (DPA) as a simple time—intensity profile from which a chemiluminescence decay rate constant could be determined. These studies demonstrated a first-order dependence for both PCPO and hydrogen peroxide and a zero-order dependence on the fluorescer in accord with an earher study (9). Furthermore, the chemiluminescence quantum efficiencies Qc) are dependent on the ease of oxidation of the fluorescer, an unstable, short-hved intermediate (r = 0.5 /is) serves as the chemical activator, and such a short-hved species "is not consistent with attempts to identify a relatively stable dioxetane as the intermediate" (68). 

The emission yield from the horseradish peroxidase (HRP)-catalyzed luminol oxidations can be kicreased as much as a thousandfold upon addition of substituted phenols, eg, -iodophenol, -phenylphenol, or 6-hydroxybenzothiazole (119). Enhanced chemiluminescence, as this phenomenon is termed, has been the basis for several very sensitive immunometric assays that surpass the sensitivity of radioassay (120) techniques and has also been developed for detection of nucleic acid probes ia dot-slot. Southern, and Northern blot formats (121). 

Autooxidation. Liquid-phase oxidation of hydrocarbons, alcohols, and aldehydes by oxygen produces chemiluminescence in quantum yields of 10 to 10 ° ein/mol (128—130). Although the efficiency is low, the chemiluminescent reaction is important because it provides an easy tool for study of the kinetics and properties of autooxidation reactions including industrially important processes (128,131). The light is derived from combination of peroxyl radicals (132), which are primarily responsible for the propagation and termination of the autooxidation chain reaction. The chemiluminescent termination step for secondary peroxy radicals is as follows ... 

Weak to moderate chemiluminescence has been reported from a large number of other Hquid-phase oxidation reactions (1,128,136). The Hst includes reactions of carbenes with oxygen (137), phenanthrene quinone with oxygen in alkaline ethanol (138), coumarin derivatives with hydrogen peroxide in acetic acid (139), nitriles with alkaline hydrogen peroxide (140), and reactions that produce electron-accepting radicals such as HO in the presence of carbonate ions (141). In the latter, exemplified by the reaction of h on(II) with H2O2 and KHCO, the carbonate radical anion is probably a key intermediate and may account for many observations of weak chemiluminescence in oxidation reactions. 

Examples include luminescence from anthracene crystals subjected to alternating electric current (159), luminescence from electron recombination with the carbazole free radical produced by photolysis of potassium carba2ole in a fro2en glass matrix (160), reactions of free radicals with solvated electrons (155), and reduction of mtheiiium(III)tris(bipyridyl) with the hydrated electron (161). Other examples include the oxidation of aromatic radical anions with such oxidants as chlorine or ben2oyl peroxide (162,163), and the reduction of 9,10-dichloro-9,10-diphenyl-9,10-dihydroanthracene with the 9,10-diphenylanthracene radical anion (162,164). Many other examples of electron-transfer chemiluminescence have been reported (156,165). 

A number of chemiluminescent reactions have been studied by producing key reactants through pulsed electric discharge, by microwave dissociation, or by observing the reactions of atoms and free radicals produced in the inner cone of a laminar flame as they diffuse into the flame s cool outer cone (182,183). These are either combination reactions or atom-transfer reactions involving transfer of chlorine (184) or oxygen atoms (181,185—187), the latter giving excited oxides. 

White Phosphorus Oxidation. Emission of green light from the oxidation of elemental white phosphoms in moist air is one of the oldest recorded examples of chemiluminescence. Although the chemiluminescence is normally observed from sotid phosphoms, the reaction actually occurs primarily just above the surface with gas-phase phosphoms vapor. The reaction mechanism is not known, but careful spectral analyses of the reaction with water and deuterium oxide vapors indicate that the primary emitting species in the visible spectmm are excited states of (PO)2 and HPO or DPO. Ultraviolet emission from excited PO is also detected (196). 

Siloxene is fluorescent and red chemiluminescence results from oxidation with ceric sulfate, chromic acid, potassium permanganate, nitric acid, and several other strong oxidants. The chemiluminescence spectmm peaks at 600 nm and has been reported (199) to give a maximum brightness of 3.43 cd/m (1 footlambert). 

Titration Indicators. Concentrations of arsenic(III) as low as 2 x 10 M can be measured (272) by titration with iodine, using the chemiluminescent iodine oxidation of luminol to indicate the end point. Oxidation reactions have been titrated using siloxene the appearance of chemiluminescence indicates excess oxidant. Examples include titration of thallium (277) and lead (278) with dichromate and analysis of iron(II) by titration with cerium(IV) (279). 

Sulfur dioxide concentrations as low as 40 mg/m in air have been determined bypassing air samples through an aqueous solution of tetrachloromercurate, which converts SO2 to the dichlorosulfitomercurate complex. Oxidation of the complex by potassium permanganate is chemiluminescent and the intensity, as measured by a photomultipHer, is proportional to sulfur dioxide concentration (312). 

Nickel Carbonyl The extremely toxic gas nickel carbonyl can be detected at 0.01 ppb by measuring its chemiluminescent reaction with ozone in the presence of carbon monoxide. The reaction produces excited nickel(II) oxide by a chain process which generates many photons from each pollutant molecule to permit high sensitivity (315). 

Ozone can be analyzed by titrimetry, direct and colorimetric spectrometry, amperometry, oxidation—reduction potential (ORP), chemiluminescence, calorimetry, thermal conductivity, and isothermal pressure change on decomposition. The last three methods ate not frequently employed. Proper measurement of ozone in water requites an awareness of its reactivity, instabiUty, volatility, and the potential effect of interfering substances. To eliminate interferences, ozone sometimes is sparged out of solution by using an inert gas for analysis in the gas phase or on reabsorption in a clean solution. Historically, the most common analytical procedure has been the iodometric method in which gaseous ozone is absorbed by aqueous KI. 

Chemiluminescence. Chemiluminescence (262—265) is the emission of light duting an exothermic chemical reaction, generaUy as fluorescence. It often occurs ia oxidation processes, and enzyme-mediated bioluminescence has important analytical appHcations (241,262). Chemiluminescence analysis is highly specific and can reach ppb detection limits with relatively simple iastmmentation. Nitric oxide has been so analyzed from reaction with ozone (266—268), and ozone can be detected by the emission at 585 nm from reaction with ethylene. 

Chemiluminescent labels, in which the luminescence is generated by a chemical oxidation step, and bioluminescent labels, where the energy for light emission is produced by an enzyme-substrate reaction, are additional labeling types (39,42). Luminol [521 -31 -3] CgHyN202, and acridine [260-94-6] C H N, derivatives are often used as chemiluminescent labels. 

Catalytic oxidation of isobutyraldehyde with air at 30—50°C gives isobutyric acid [79-31-2] ia 95% yield (5). Certain enzymes, such as horseradish peroxidase, cataly2e the reaction of isobutyraldehyde with molecular oxygen to form triplet-state acetone and formic acid with simultaneous chemiluminescence (6). 

The NO analyzer is based on the principles of chemiluminescence to determine continuously the NO concentration in the sample gas stream. The analyzer should contain a NOg-to-NO converter, which converts the nitrogen dioxide (NO9) in the sample gas to nitrogen oxide (NO). An NOg-to-NO converter is not necessary if data are presented to demonstrate that the NO9 portion of the exhaust gas is less than 5 percent of the total NO9 concentration. 

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