Chemiluminescence elicitation from an O 2 and/or HOOH complex of the riboflavin-copper(I)-chelate

Stone, Michael O.; Vorhaben, Jean E.; Steele, Richard

doi:10.1016/0006-291x(69)90593-2

Cited by 3 publications

(10 citation statements)

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“…Vorhaben (1965) reported that all the H2A was exhausted in less than 1 min in such systems, but it is possible that the ascorbate oxidation products or the ascorbate semiquinone-copper-oxygen complex proposed by Khan and Martell (1967) have much longer lifetimes. As reported by us in an earlier paper (Stone et al, 1969), the pseudo-first-order rate constants for the chemiluminescent decay elicited from an incubation system are relatively unchanged over a considerable portion of the incubation period. It is consequently figure 5: Maximum chemiluminescence and glow vs. incubation time from a system containing riboflavin (0.46 Mmole), ascorbic acid (8 Mmoles), Cu(II) (3 Mmoles), P04 buffer (pH 6.2, 4 mmoles), under 100% Oj at 1 atm.…”

Section: Resultssupporting

confidence: 66%

“…This potential not only increased very rapidly, it yielded much more chemiluminescence, by an order of magnitude, than a comparable system incubated under a lower p 0 2 (cy. Stone et al, 1969, Figure 1). Since the chemiluminescence potential of a standard incubation system was enhanced so greatly by an increase in O2 tension, the use of pure 0 2 was instituted routinely in order to obtain the greatest concentration of the chemiluminescent compound in the least time for all other experiments involving the oxygenated system.…”

Section: Resultsmentioning

confidence: 98%

“…have presented data to indicate that the luciferin reacts with 0 2 to produce an intermediate which reacts then with aldehyde to yield light. Since Vorhaben (1965) and Stone and Steele (1969) have shown that F M N can be substituted for riboflavin in the generation of the chemiluminescent compound it was of interest to determine whether the compound would react with the bacterial luciferase to give light. When the chemiluminescent compound generated in either a riboflavin or F M N incubation system was oxygenated, reacted with dodecylaldehyde (Aldrich Chemical Co.), solubilized by sonication, and then injected with the luciferase, no chemiluminescence was elicited.…”

Section: Resultsmentioning

confidence: 99%

“…In a preliminary report Stone and Steele (1969) presented evidence that X was peroxidic in nature and possibly a hydroperoxide of riboflavin. In a later paper ,Stone et af.…”

mentioning

confidence: 99%

“…In a preliminary report Stone and Steele (1969) presented evidence that X was peroxidic in nature and possibly a hydroperoxide of riboflavin. In a later paper ,Stone et al (1969) presented evidence for the generation of X via a riboflavin-copper® chelate intermediate which reacted with 02 and/or HOOH to produce an 02 and/or HOOH adduct.…”

mentioning

confidence: 99%

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Chemiluminescence from an oxygen and/or hydrogen peroxide. Adduct derived from the riboflavin-copper(I) chelate

Mo¹,

Rh²

1970

Biochemistry

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This paper characterizes a biochemical redox system from which a chemiluminescence can be elicited by injection of HOOH. This system consists of an aqueous solution of riboflavin, ascorbic acid, and copper(II), i 02, which is buffered with phosphate at a pH of 6.2. Evidence is presented which indicates the generation of the riboflavincopper(1) chelate in the system. The riboflavin-copper(1) chelate is believed to form an 0 2 "adduct" with molecular O2 to produce the compound which can react with HOOH to give chemiluminescence, presumably via an O2 and/or HOOH adduct of the riboflavin-copper(1) chelate. The riboflavin-copper(1) chelate was prepared independently, 502, and found to possess absorption and chemiluminescent spectra similar to those of the riboflavin-copper(I1)-ascorbic I n 1941, Szent-Gyorgyi proposed that electronic excited states might be utilized in a general way in the metabolism of living organisms, in addition to their well-known participation in bioluminescence, photosynthesis, and vision. Bioluminescence is chemiluminescence in vivo and when light in the visible spectrum is seen, it is evidence that electronic excited states with energies up to 80 kcal (3.5 eV) are produced. If the energy of electronic excited states is to serve an organism in a general manner, two basic criteria must be met: (1) the electronic excited states must be generated chemically in thq dark, and (2) the energy generated must be utilized in some cellular function and not lost as heat or fight.In this respect, it was shown by Vorhaben (1965) and Vorhaben and Steele (1967) that, in at least one case, electronic excited states can be generated in a model nonbioluminescent biochemical redox system. This system consisted of riboflavin, ascorbic acid, cupric ions, HOOH, and phosphate buffer (pH 6. l), all in concentrations within physiological ranges. In connection with this work, Vorhaben (1965) discovered that this system without HOOH showed an increase in the elicitable chemiluminescence, with respect to the time of incubation under 02, upon subsequent addition of HOOH. This indicated the generation of a relatively stable intermeacid system, i 02. Reduced nicotinamide-adenine dinucleotide was found to substitute successfully for ascorbic acid. When glucose and glucose oxidase, as a HOOH feeder system, were "coupled" to the oxygenated riboflavin-copper(1) chelate, from either of the cited sources, a low-level chemiluminescence ("glow") was observed which showed firstorder dependence upon the 0 2 concentration. Flavin mononucleotide, rhodamine B, and pyronine B were found to yield chemiluminescence when substituted for riboflavin in the riboflavin-copper(I1)-ascorbic acid system. Mechanisms are proposed for the generation of the riboflavin-copper(1) chelate in biochemical systems and its subsequent reaction with O2 and/or HOOH to produce the species which yields light with excess HOOH.diate, X, 1 which perhaps could be isolated and characterized. The identity of X is fundamental to the question of the mechanism of the chemi...

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Section: Resultssupporting

confidence: 66%

Section: Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 99%

“…In a preliminary report Stone and Steele (1969) presented evidence that X was peroxidic in nature and possibly a hydroperoxide of riboflavin. In a later paper ,Stone et af.…”

mentioning

confidence: 99%

mentioning

confidence: 99%

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