Indirect chemiluminescence by 1,2-dioxetanes. Evaluation of triplet-singlet excitation efficiencies. Long range singlet-singlet energy transfer and an efficient triplet-singlet energy transfer

Turro, Nicholas J.; Lechtken, Peter; Schuster, Gary B.; Orell, Jeffrey; Steinmetzer, Hans‐Christian; Adam, Waldemar

doi:10.1021/ja00812a076

Cited by 66 publications

(23 citation statements)

References 3 publications

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“…Moreover, chemiluminescence and the rate of glutathione release were found, in a series of four perfused livers, to be statistically correlated (r = 0.90; P <0.1). DISCUSSION Chemiluminescence, glutathione release (2), and evolution of hydrocarbons (26,27) Russell's (30) or Pryor's (31) mechanism, and (ii) the formation of 1,2-dioxetane derivatives either from the lipid peroxidation free radical process or from the reaction of singlet oxygen with double bonds that makes likely the generation of excited carbonyl groups after rupture of the carbon-carbon and oxygen-oxygen linkages (32)(33)(34)(35). Experimental evidence for the generation of singlet oxygen has been obtained mainly through the effect of specific quenchers (14,15,36) or spectral analysis (10) in biological or model systems.…”

Section: Methodsmentioning

confidence: 99%

Organ chemiluminescence: noninvasive assay for oxidative radical reactions.

Boveris¹,

Cadenas²,

Reiter³

et al. 1980

Proc. Natl. Acad. Sci. U.S.A.

293

171

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In situ and perfused rat livers showed a spon- .) The existence of such light emission, which should be termed "low-level chemiluminescence" to differentiate it from the more effective photoemission of the luciferin/luciferase systems (5, 6), was soon related to oxygendependent chain reactions involving biological lipids (3-5). This early work lay fallow for years, notwithstanding the reports by Stauff and Ostrowski on the chemiluminescence of mitochondria (7) and Howes and Steele on the chemiluminescence of microsomes (8, 9), both isolated from rat liver. The more recent reports by Nakano et al. (10) and Sugioka and Nakano (11) of light emission during lipid peroxidation and other oxidative reactions (12) in microsomes revived interest in the phenomenon and suggested chemiluminescence as a tool for the investigation of the radical reactions of lipid peroxidation under physiological conditions. We have recently reported that maximal light emission in isolated mitochondria and microsomes (13) and in submitochondrial particles (14) requires an electron transfer system, hydroperoxide, and oxygen, and that hydroperoxide-supplemented cytochrome c provides a chemiluminescent model system suitable for the elucidation of some of the molecular mechanisms responsible for light emission (15). On the other hand, isolated cells such as amoebae (16) and phagocytizing leukocytes (17) also have been found to be effective chemiluminescent sources.The most important aspect of the organ chemiluminescence is that it gives readily detectable, continuously monitorable, noninvasive signals of oxidative metabolism. This article explores the possibility of continuously monitoring the metabolism of exposed or fiberoptic probed organs in vivo by the chemiluminescent technique. In this paper we report the spontaneous and hydroperoxide-induced chemiluminescence of the in situ and perfused rat liver, as well as a partial spectral analysis of the chemiluminescence of the perfused liver. Light emission seems to indicate the generation of shkrt-lived free radicals and excited states derived from the side reactions of the free radical process of lipid peroxidation. A preliminary report on light emission has been published elsewhere (13). MATERIALS AND METHODSPhoton Counting. A single-photon-counting apparatus was used (Fig. 1). Both an EMI 9658 photomultiplier, responsive in the range 300-900 nm, with an applied potential of -1.2 kV (dark current: 20-30 counts per second), and an RCA 8850 photomultiplier, responsive in the range 300-650 nm, with an applied potential of -1.8 kV (dark current: 300-400 counts per second) were used. Phototube output was connected to an amplifier-discriminator (model 1121; Princeton Applied Res., Princeton, NJ) adjusted for single photon counting and connected to both a frequency counter (Heathkit IB 1100, Heath, Benton Harbor, MI) and a recorder. The EMI phototube, cooled .down to -400C by a thermoelectric cooler (EMI-Gencom, Plainview, NY) and the RCA phototube were placed in an Ortec housing, sealed and su...

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Section: Methodsmentioning

confidence: 99%

Organ chemiluminescence: noninvasive assay for oxidative radical reactions.

Boveris¹,

Cadenas²,

Reiter³

et al. 1980

Proc. Natl. Acad. Sci. U.S.A.

293

171

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“…The very low rate of decomposition compared with those of all other known dioxetanes was attributed to a steric effect (17). Unsymmetrically substituted dioxetanes which bear a single adamantyl group decompose more rapidly than the bisadamantyl derivatives but are sufficiently stable for commercial applications, e.g., in clinical assays.…”

Section: Chemiluminescent Assaymentioning

confidence: 97%

Clinical applications of luminescent assays for enzymes and enzyme labels

Bronstein¹,

Kricka

1989

Clinical Laboratory Analysis

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A wide range of luminescent assays for enzyme labels has been developed. The clinical application of luminescent assays for horseradish peroxidase, alkaline phosphatase, xanthine oxidase, beta-D galactosidase, and glucose 6-phosphate dehydrogenase is discussed. The enzyme luminescent methods provide improved sensitivity compared with colorimetric and fluorimetric assays. A new reagent, dioxetane phosphate, has provided a simple and extremely sensitive assay for alkaline phosphatase. The available instruments and new photographic detection techniques for luminescent assays are briefly discussed.

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“…Hence, Schuster and collaborators inferred that light emission was resulting from an electron transfer mechanism instead of by energy transfer and named this process activated (or catalyzed ) chemiluminescence. On the basis of results obtained mainly by the research groups of Adam and Schuster, the elegant chemically initiated electron exchange luminescence (CIEEL, Scheme ) mechanism was proposed to rationalize the chemiexcitation of carbonyl compounds upon catalyzed decomposition of 1,2‐dioxetanones, marking the beginning of the golden age of studies on chemiluminescence and bioluminescence.…”

Section: The (Bio)chemistry Of Four‐membered Ring Peroxidesmentioning

confidence: 99%

Four‐membered cyclic peroxides: Carriers of chemical energy

Bastos

Farahani

Bechara

et al. 2017

J of Physical Organic Chem

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Four-membered cyclic peroxides are high-energy compounds often associated to cold light emission, but whose chemical and biological roles are still matters of debate. The often-dangerous synthesis of 1,2-dioxetanes, achieved around 50 years ago, has been mastered over the years to a point where some derivatives are commercially available. This fact does not imply that 1,2-dioxetanes can be conveniently prepared in the gram scale or that the synthesis of analogous 1,2-dioxetanones and the elusive 1,2-dioxetanedione are simple. Important questions on the mechanism of chemiluminescence and bioluminescence reactions are under experimental and theoretical scrutiny. The available data have contributed to relate structural and medium effects to the quantum efficiency of these compounds to produce excited states. Consequently, such peroxides have been suggested to produce biologically relevant electronically excited species in vivo in the absence of light. The connection of this hypothesis with melanin-mediated photodamage in the dark has renewed the interest in such cyclic peroxides. This review gives some insight on the synthesis, chemiluminescence mechanism, and biological relevance of 1,2-dioxetanes, 1,2-dioxetanones, and 1,2-dioxetanedione and provides practical protocols for those interested in engaging this field.

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Indirect chemiluminescence by 1,2-dioxetanes. Evaluation of triplet-singlet excitation efficiencies. Long range singlet-singlet energy transfer and an efficient triplet-singlet energy transfer

Cited by 66 publications

References 3 publications

Organ chemiluminescence: noninvasive assay for oxidative radical reactions.

Organ chemiluminescence: noninvasive assay for oxidative radical reactions.

Clinical applications of luminescent assays for enzymes and enzyme labels

Four‐membered cyclic peroxides: Carriers of chemical energy

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