Chemiluminescence-kinetics

Equation (13) appears to be a good approximation for describing isothermal chemiluminescence kinetics for homogeneous systems where oxidation takes place uniformly. However, as has been shown by several authors [53-58], the different sections of a polymer sample may oxidize with its autonomous kinetics determined by different rates of primary initiation. A chemiluminescence imaging technique revealed that the light emission may be spread from some sites of the polymer film and the isothermal chemiluminescence vs. time runs are then modified, particularly in the stage of an advanced oxidation reaction [59]. 

Finlayson, B. J., J. N. Pitts, Jr., and R. Atkinson. Low-pressure gas-phase ozone-olefin reactions. Chemiluminescence, kinetics, and mechanisms. J. Amer. Chem. Soc. % 5356-5357, 1974. 

The main features of the chemiluminescence mechanism are exemplarily illustrated in Scheme 11 for the reaction of bis(2,4,6-trichlorophenyl)oxalate (TCPO) with hydrogen peroxide in the presence of imidazole (IMI-H) as base catalyst and the chemiluminescent activators (ACT) anthracene, 9,10-diphenylanthracene, 2,5-diphenyloxazole, perylene and rubrene. In this mechanism, the replacement of the phenolic substituents in TCPO by IMI-H constitutes the slow step, whereas the nucleophilic attack of hydrogen peroxide on the intermediary l,l -oxalyl diimidazole (ODI) is fast. This rate difference is manifested by a two-exponential behavior of the chemiluminescence kinetics. The observed dependence of the chemiexcitation yield on the electrochemical characteristics of the activator has been rationalized in terms of the intermolecular CIEEL mechanism (Scheme 12), in which the free-energy balance for the electron back-transfer (BET) determines whether the singlet-excited activator, the species responsible for the light emission, is formed ... 

Based on the kinetic results of experiments with photoinitiated peroxyoxalate chemiluminescence, Milofsky and Birks proposed, for the first time, the involvement of a six-membered cyclic peroxide (51) as HEI. On the basis of this suggestion, Hadd and coworkers, using conventional chemiluminescent kinetic studies with 47, also proposed the involvement of two HEIs, 48 and another six-membered cyclic peroxide 52 similar to 51. 

The chemiluminescent kinetics are second-order in TMAE and can be written... 

Yu.A. Vladimirov, Studies of the antioxidant activity by measuring chemiluminescence kinetics. In L. Packer, M.G. Traber and W. Xin, (eds.). Molecular Mechanisms and Health Effects. Champaign, Illinois, 1996, pp. 125-144. 

Fig. 1. Chemiluminescence kinetics of PMA-stimulated luminol enhanced neutrophils in calves within day 1 and day 4 after birth (lower panel). The Y axis is the cumulative RLU / s in function of time and the X axis is the entire measurement period of CL. Carve is mean of 5 calves. Light microscopic image of neonatal whole blood (upper left x 1000, showing immature neutrophils) and isolated neutrophils (upper right x 400 appearance of apoptotic neutrophils).

Svir IB, Oleinick AI (2(X)1) The electrogenerated chemiluminescence kinetics at a microdisk electrode. J Electroanal Chem 499 30-38... 

Carrington T and Polanyi J C 1972 Chemiluminescent reactions Chemical Kinetics, Int. Rev. Sc/. Physical Chemistry senes 1, vol 9, ed J C Polanyi (London ButtenA/orths) pp 135-71... 

In addition to ready thermal decomposition, 1,2-dioxetanes are also rapidly decomposed by transition metals (39), amines, and electron-donor olefins (10). However, these catalytic reactions are not chemiluminescent as determined by the temperature drop kinetic method. 

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). 

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 ... 

Decomposition of diphenoylperoxide [6109-04-2] (40) in the presence of a fluorescer such as perylene in methylene chloride at 24°C produces chemiluminescence matching the fluorescence spectmm of the fluorescer with perylene was reported to be 10 5% (135). The reaction follows pseudo-first-order kinetics with the observed rate constant increasing with fluorescer concentration according to = k [flr]. Thus the fluorescer acts as a catalyst for peroxide decomposition, with catalytic decomposition competing with spontaneous thermal decomposition. An electron-transfer mechanism has been proposed (135). 

The verification of theoretical data obtained by simulation of peroxide oxidation kinetics of macromolecules with experimental data, obtained from chemiluminescent analysis of blood using automated complex ChLC-1. This automated complex was developed by the authors and laboratory colleagues. 

Anions of another group were derivatized with formation of gaseous chemiluminescing species. Chemical reaction - gas extraction has been used with chemiluminescence detection in the stream of canier gas in on-line mode. Rate of a number of reactions has been studied as well as kinetic curves of extraction of gaseous products. Highly sensitive and rapid hybrid procedures have been developed for the determination of lO, BrO, CIO, CIO, NO,, N03, CrO, CIO, Br, T, S, 803 with detection limits at the level of pg/L, duration of analysis 3 min. 

The reactivity of NO towards atoms, free radicals, and other paramagnetic species has been much studied, and the chemiluminescent reactions with atomic N and O are important in assaying atomic N (p. 414). NO reacts rapidly with molecular O2 to give brown NO2, and this gas is the normal product of reactions which produce NO if these are carried out in air. The oxidation is unusual in following third-order reaction kinetics and, indeed, is the classic... 

Instrumental methods of peroxide analysis feature polarography, which is used to detn hydroperoxides, peroxyesters and diacyl peroxides as well as dicyclohexyl peroxydicarbonate in polystyrene. Other techniques include infrared (800 to 900cm 1) chemiluminescent analysis for kinetic studies, and chromatography for the identification and separation of peroxides in complex mixts (Refs 5,6, 7,14,15,16,17, 20 21)... 

In order to optimize the chemiluminescence response, we have investigated the mechanism of the complex reactions leading to chemical generation of chemiluminescence. A new peroxyoxalate-hydrogen peroxide reaction mechanism has emerged from our preliminary studies on the five contributing factors listed above. Two kinetic models are discussed, one for the... 

Figure 10. Simulated decay curves from the kinetic analysis of the TCPO-H2O2-DPA chemiluminescence. Arbitrary units (a.u.) used on both axes. (Reproduced from Ref. 24. Copyright 1986 American Chemical Society.)...

Another approach to the determination of surface kinetics in these systems has been to combine molecular beams in the 10 2-10 1 mbar pressure range with the use of the infrared chemiluminescence of the C02 formed during steady-state NO + CO reactions. This methodology has been used to follow the kinetics of the reaction over Pd(110) and Pd(l 11) surfaces [49], The activity of the NO + CO reaction on Pd(l 10) was determined to be much higher than on Pd(lll), as expected based on the UHV work discussed in previous sections but in contrast with result from experiments under higher pressures. On the basis of the experimental data on the dependence of the reaction rate on CO and NO pressures, the coverages of NO, CO, N, and O were calculated under various flux conditions. Note that this approach relied on the detection of the evolution of gas-phase... 

Chemiluminescence is light emission from the relaxation of electrons populating excited states in an elementary step of a chemical reaction. Since, the process of population of excited states is related kinetically to the kinetics of the given chemical reaction, the emission of chemiluminescence over time should thus be related to the rate of the chemical reaction. 

The intensity of chemiluminescence signal from a heated polymer and the kinetics of its change with time or temperature is determined by [30] ... 

Comparison of chemiluminescence isothermal runs with oxygen uptake and DSC measurements has been at the centre of interest since practical industrial applications of the chemiluminescence method were attempted. It is a fact that the best comparison may be achieved when studying polymers that give a distinct induction time of oxidation typical for autoaccelerating curves of a stepwise developing oxidation. This is the particular case of polyolefins, polydienes and polyamides. The theoretical justification for the search of a mutual relationship between the oxidation runs found by the various methods follows directly from the kinetic analysis of the Bolland-Gee scheme of polymer oxidation. 

G.A. George, Use of chemiluminescence to study the kinetics of oxidation of solid polymers. In N. Grassie (Ed.), Developments in Polymer Degradation-3, Applied Science Publishers, London, 1981, p. 173. 

M. Ayyagari, S. Kametkar, R. Pande, K.A. Marx, J. Kumar, S.K. Tripathy, J. Akkara, and D.L. Kaplan, Chemiluminescence-based inhibition kinetics of alkaline phosphatase in the development of a pesticide biosensor. Biotechnol. Prog. 11, 699-703 (1995). 

The fact that the kinetic chain length of dimedone autoxidation is very low appears to indicate structural effects in autoxidation reactions. These may account for some of the discrepancies found in autoxidation chemiluminescence studies of different types of compounds. 

Oxygen radical anion forms excited-singlet oxygen in different pathways, e.g. by a reaction with copper-cysteine-oxygen complex to yield the excimer (02)2- The computerized kinetic equations derived from this scheme allowed predictions in respect of the chemiluminescence intensity as a function of the oxygen and cysteine concentrations and as a function of time these were satisfactorily confirmed by the ex-... 

The reaction of Ru(III) chelate with diimine is about 99 times more efficient than that of Ru(III) with hydrazine. Computer-simulated chemiluminescence time curves based on the kinetic data of the above reaction scheme exactly matched light-intensity time curves recorded in a stopped-flow spectrophotometer 166h At high hydrazine concentra-... 

Seitz, Suydam, and Hercules 186> recently developed on the basis of luminol chemiluminescence a method for chromium-III ion determination which has a detection limit of about 0.025 ppb. The method is specific for free chromium-III ions as chromium-VI compounds have no catalytic effect and other metal ions can be converted to a non-catalytic form by complexing with EDTA, since the chromium-III complex of EDTA, which is in any case not catalytically active, is formed kinetically slowly 186>. To detect extremely small light emissions, and hence very small metal concentrations, a flow system was used which allows the reactants to be mixed directly in front of a multiplier. (For a detailed description of the apparatus, see 186>). 

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