Total Chemiluminescence Research Articles

Enhancer effect of fluorescein on the luminol-H2O2-horseradish peroxidase chemiluminescence: energy transfer process.

The chemiluminescence of the luminol-H2O2-horseradish peroxidase system is increased by fluorescein. Fluorescein produces an enhancement of the luminol chemiluminescence similar to that of phenolphthalein, by an energy transfer process from luminol to fluorescein. The maximum intensity and the total chemiluminescence emission (between 380 and 580 nm) of luminol with fluorescein was more than three times greater than without fluorescein; however, the emission duration was shorter. The emission spectra in the presence of fluorescein had two maxima (425 and 535 nm) and the enhancement was dependent on pH and fluorescein concentration. A mechanism is proposed to explain these effects.

Kupffer cells generate superoxide anions and modulate reperfusion injury in rat livers after cold preservation

This study was designed to determine the source of reactive oxygen species (ROS) and whether Kupffer cells modulate the injury of perfused rat liver after cold preservation. The livers of male Lewis rats pretreated with schizophyllan glucan (SPG) (10 mg/kg, SPG group) or gadolinium chloride (5 mg/kg; Gd group) and untreated rats (control group) were preserved in University of Wisconsin solution for 0, 12, and 24 hours at 4 degrees C and then perfused for 60 minutes with oxygenated Krebs-Henseleit bicarbonate buffer. Real-time chemiluminescence (CL) of the liver during perfusion was measured using a sensitive photomultiplier, and reperfusion injury was assessed by measuring lipid peroxidation and lactate dehydrogenase release. CL intensity reached a peak within 5 minutes of reperfusion, and superoxide dismutase completely inhibited this CL in all groups. In the control group, the total CL intensity was high after 24 hours of preservation. It significantly (P < .05 vs. control group) increased in the SPG group, while it decreased in the Gd group after 12 and 24 hours of preservation. The total CL intensity decreased by 70% (when diphenyliodonium chloride (100 micromol/L; an NADPH oxidase inhibitor) was added to the perfusate before preservation of untreated rats. Lipid peroxidation and lactate dehydrogenase release significantly (P < .05) deteriorated in the SPG group, while they ameliorated in the Gd group after 24 hours of preservation. These results demonstrate that Kupffer cells primarily generate superoxide anions and modulate the organ injury in the initial phase of reperfusion after cold preservation.(Hepatology 1997 Feb;25(2):356-60)

Kupffer Cells Generate Superoxide Anions and Modulate Reperfusion Injury in Rat Livers After Cold Preservation

ABSTRACT This study was designed to determine the source of reactive oxygen species (ROS) and whether Kupffer cells modulate the injury of perfused rat liver after cold preservation. The livers of male Lewis rats pretreated with schizophyllan glucan (SPG) (10 mg/kg, SPG group) or gadolinium chloride (5 mg/kg; Gd group) and untreated rats (control group) were preserved in University of Wisconsin solution for 0, 12, and 24 hours at 4 degrees C and then perfused for 60 minutes with oxygenated Krebs–Henseleit bicarbonate buffer. Real–time chemiluminescence (CL) of the liver during perfusion was measured using a sensitive photomultiplier, and reperfusion injury was assessed by measuring lipid peroxidation and lactate dehydrogenase release. CL intensity reached a peak within 5 minutes of reperfusion, and superoxide dismutase completely inhibited this CL in all groups. In the control group, the total CL intensity was high after 24 hours of preservation. It significantly ( P &lt; .05 vs. control group) increased in the SPG group, while it decreased in the Gd group after 12 and 24 hours of preservation. The total CL intensity decreased by 70% (when diphenyliodonium chloride (100 micromol/L; an NADPH oxidase inhibitor) was added to the perfusate before preservation of untreated rats. Lipid peroxidation and lactate dehydrogenase release significantly ( P &lt; .05) deteriorated in the SPG group, while they ameliorated in the Gd group after 24 hours of preservation. These results demonstrate that Kupffer cells primarily generate superoxide anions and modulate the organ injury in the initial phase of reperfusion after cold preservation.

Characterisation of polypropylene peroxides; their thermo-oxidative stability and reactivity towards dimethylsulfide

Exposure to dimethylsulfide (DMS) has previously been presented as a tool to distinguish between different types of polypropylene (PP) peroxides. The reasons for the differences in peroxide reactivity towards DMS are investigated for PP peroxides. This was accomplished using iodometry, infrared spectroscopy, measurements of total emitted chemiluminescence, chemiluminescence imaging and measurements of glass transition and melting temperatures. On the basis of our results, we propose that DMS reacts preferentially with peroxides which are adjacent to each other, rather than with isolated peroxides. The higher reactivity of adjacent peroxides towards DMS is believed to be due to a catalytic action of protic species. An increase in glass transition temperature during oxidation was observed, which indicates an increasingly restricted segmental mobility. Furthermore, changes in concentration of DMS-resistant peroxides during oxidation were found to correlate with the changes in glass transition and melting temperatures. Consequently, we propose that the segmental mobility in the polymer affects the reactivity of the isolated peroxides towards DMS.

Analytical detection system of mixed odor vapors using chemiluminescence-based gas sensor

A chemiluminescence(CL)-based gas sensor made of γ-Al 2O 3 emits CL during catalytic oxidation of a combustible odor vapor. The CL intensity is proportional to the concentration of ethanol or acetone vapor in air. The algebraic sum rule is applicable to the CL intensities by the mixed gas of these two kinds of vapors, when the sensor is heated above 450°C. The CL intensities are measured in periodic temperature cycles between 650 and 450°C. The concentrations of vapor components can be detected analytically by measuring total CL intensities during the high and low temperatures for air containing mixed vapors of various concentrations of ethanol below 400 ppm and acetone below 200 ppm.

Electronic branching ratios in the chemiluminescent reactions of Ca( 1S) and Ca ∗( 3P) with ICl and IBr

Chemiluminescence of calcium monohalides formed in the reactions of ground state Ca( 1S) and metastable Ca ∗( 3P) atoms with ICl or IBr was studied in a beam-gas arrangement. Total collision and chemiluminescence cross sections were measured to estimate photon yields of electronic states of the products. For the (A 2Π+B 2Σ +) states, aggregate yields appear to be arithmetic averages of the values for proper homonuclear halogen targets and branching ratios are in agreement with prior expectations. The experiment gives lower limits of the dissociation energies: D 0(CaBr) ⩾ 353 kJ/mol and D 0(CaI) ⩾293 kJ/mol.

Continuous determination and discrimination of mixed odour vapours by a new chemiluminescence-based sensor system

A gas sensor that utilizes chemiluminescence (CL) during the catalytic oxidation of odour vapours on a sintered aluminium oxide (γ-Al 2O 3) layer is proposed. A new technique is applied to determine continuously the concentration of each constituent in a mixed vapour by a single CL-based sensor. The sensor is heated and cooled periodically in a temperature cycle between 200 and 740 °C at constant heating and cooling rates of ±9 °C s −1. By measuring the total CL intensities in the heating and cooling courses, we can obtain the concentration of each constituent for a mixed vapour of ethanol and acetone in air. The lowest detection limit of the concentration of these vapours is of the order of 1 ppm.

Chemiluminescence of alkaline earth monoiodides in collisions of metastable Mg, Ca and Sr atoms with I 2

Chemiluminescence of MgI, CaI, and SrI was observed in a beam-gas arrangement when atomic beams of Mg, Ca, and Sr were excited to the 3P J states. Total collision and chemiluminescence cross sections were measured. For MgI, in the region of the a 2Π-X 2Σ + transition reported from absorption experiments, only a weak unstructured band was observed; photon yield of this emission was determined to be 0.013%. For CaI, the A, B, C-X chemiluminescence spectra have a total photon yield of 15%. Unknown emission of strontium monoiodide in the 600–630 nm range is tentatively attributed to the A′ 2Δ-X 2Σ + transition.

In vitro immunomodulation by pentachlorophenol in phagocytes from an estuarine teleost, Fundulus heteroclitus, as measured by chemiluminescence activity

Chemiluminescence (CL) was used to assay effects of pentachlorophenol (PCP) on the production of reactive oxygen intermediates (ROIs) generated by leukocytes from an estuarine teleost, Fundulus heteroclitus. Two parameters were measured during the phagocytically-induced respiratory burst: peak CL (maximal value) and total CL (temporal summation of induced values). Phagocytes obtained from the pronephros were incubated in the presence of sublethal doses of analytical (A-) or technical (T-) grades of PCP. Technical PCP has been reported to be more highly immunosuppressive than A-PCP in mammals; this effect was attributed to dioxins and other contaminants produced during manufacture. In this fish, both grades of the compound produced significant dose-dependent inhibition of peak and total CL. However, there were few significant differences between the effects of the two PCP grades on the magnitude of the CL responses at identical, sublethal concentrations, although T-PCP did produce a more marked reduction in the relative level of leukocytic CL as a function of dose than did A-PCP. Because of the probable roles of ROIs in antimicrobial blood cell-mediated mechanisms, reduced CL activity was interpreted as an indication of xenobiotic-induced immunosuppression.

Peroxidase-catalyzed co-oxidation of indole-3-acetic acid and xanthene dyes in the absence of hydrogen peroxide

The effect of xanthene dyes on the chemiluminescence from the aerobic indole-3-acetic acid (IAA) oxidation, catalyzed by horseradish peroxidase (HRP), was studied. The rate of IAA oxidation and dye destruction were controlled. It was found that the addition of dyes to the IAA/HRP/O 2 system resulted in: (i) the appearance of emission in the region of dye fluorescence, (ii) an increase of the total chemiluminescence intensity, (iii) a decrease of the emission duration, (iv) the acceleration of IAA oxidation, and (v) slow bleaching of the dyes. The experimental results lead to the conclusion that all spectral and kinetic variations of the chemiluminescence from the IAA/HRP/O 2 system which are caused by the addition of xanthene dyes, are the result of IAA-dye co-oxidation. Earlier published reports regarding energy transfer from electronically excited species, generated in the IAA/HRP/O 2 system, to the xanthene dyes seem to be erroneous.

Oxyradical Generation from Leukocytes during Endotoxin-Induced Microcirculatory Disturbance in Rat Mesentery-Attenuating Effect of Cetraxate

By using the intravital microscope equipped with digital imaging processor, we investigated the granulocyte-mediated oxidative burst during the endotoxin-induced microvascular derangement in rat mesentery. The leukocyte behavior after the injection of acridine orange was detected by using a silicon-intensified target camera, the erythrocyte velocity was measured by using a high-speed video camera system, and the luminol-dependent photoemission was visualized by an ultrasensitive photon-counting camera in lipopolysaccharide (LPS)-treated micro-vascular beds. At 60 min after the LPS administration, a significant leakage of FITC-labeled albumin was observed along mesenteric venules under a fluorescence microscopy. The number of sticking leukocytes increased in association with the decrease in erythrocyte velocity after starting the LPS infusion. The luminol-dependent chemiluminescence in microvascular beds gradually increased over that recorded prior to LPS exposure and was fourfold higher 60 min after the start of LPS infusion. The distribution of the photoemission clearly corresponded to the venular endothelium, to which leukocytes adhered. In blood samples taken from the mesenteric vein at 60 min after the LPS administration, a decrease in the number of granulocytes and increases of total and individual chemiluminescence activities were observed. These results suggest that LPS induces oxidative burst from granulocytes on the venular endothelium. Cetraxate, an inhibitor of proteases including plasmin, significantly inhibited the leukocyte activation and prevented alterations in microvascular hemodynamics induced by LPS in vivo, whereas it had no effect on the LPS-induced oxyradical generation from adherent leukocytes in vitro. The present study demonstrates that proteases such as plasmin may play an important role in the pathogenesis of endotoxin-induced microvascular disturbances.

Differential activation of polymorphonuclear leukocytes from peripheral blood and exudate in surgical patients.

We examined the effects of surgical trauma on polymorphonuclear leukocyte (PMN) chemotaxis, production of phagocytosis-dependent intracellular chemiluminescence (CL) and production of phagocytosis-independent total CL in two groups: group A with esophageal cancer, and group B with gastric cancer. The scale of surgical trauma was quantified by measuring interleukin-6 in plasma and exudate from drainage tubes. We found a significant augmentation of chemotaxis, total CL and intracellular CL in both groups during the post-operative week. In group A, the increments in both chemotaxis and total CL of circulating cells were smaller than those in group B, but there was no significant difference in intracellular CL between the two groups. Exudate PMNs were more chemotactic, but produced smaller amounts of total CL than circulating cells. No significant difference in intracellular CL between exudate and circulating PMNs was detected, indicating that phagocytic activity was not affected. We conclude that severe surgical trauma causes circulating PMNs with high chemotactic activity to migrate to sites of injury, but that preactivated PMNs in exudate examined in vitro produce lower amounts of reactive oxygen metabolites in response to soluble chemoattractants in vitro than cells circulating in plasma.

The very fast chemiluminescent reaction I(5p 52P [formula omitted]) + I(5p 52P [formula omitted]) → (M) I 2(B O u+, υ′) → I 2(X O g+, υ″) + hν

The method of quantitative laser induced chemiluminescent kinetic spectroscopy (QLICKS) is developed for the study of chemiluminescence reactions. This method enables us to determine spectral distributions of chemiluminescence rate constants k cl(λ) (photon cm 3/particle 2 s nm) and total chemiluminescence rate constants k cl (photon cm 2/particle 2 s). QLICKS is applied to the study of the iodine atom recombination accompanied by radiation according to I(5p 5 2P 1 2 ) + I(5p 5 2P 3 2 ) → (M) I 2(B O u +, υ′) → I 2(X O g +, υ″) + hν (i). Iodine atoms are obtained by photolysis of RI = CF 3I, CF 3CFICF 3 at λ = 266 nm. Assuming quantum yields of the I( 2P 3 2 ) and I( 2P 1 2 ) atoms formation equal to 0.1 and 0.9, respectively, the following values of the total chemiluminescence rate constant are determined: k i = (10 +10 −5, 7.4 +7 −4 and 3.0 +3 −1.6) × 10 −15 photon cm 3/particle 2 s for M = He, Ar and CF 3CFICF 3 respectively. The rate constant of the process 2I(5p 5 2P 1 2 ) → (M) I 2(1 u) → I 2(1 g) + hν (ii) is estimated to be k ii = (3.5 +3.5 −1.7) × 10 −17 photon cm 3/particle 2 s for M = CF 3I, CF 3CFICF 3. Kinetic and spectral features of reaction (i) can be described only in terms of the I*…M or I…M complex formation. Process (i) may be considered as representative of a wide class of recombination reactions accompanied by radiation proceeding through complex formation with a particle M and having very high rate constants. The existence of such very fast chemiluminescent reactions provides real opportunities for the development of recombination lasers operating on molecular transitions.

Increased oxygen free radical activity in patients on cardiopulmonary bypass undergoing aortocoronary bypass surgery

Cardiac dysfunction after cardiopulmonary bypass (CPB) has been reported by various investigators. Oxygen free radicals have been shown to depress cardiac function and contractility. To evaluate the possible role of oxygen free radicals (OFR) in post-pump cardiac dysfunction, measurements of cardiac function, OFR producing activity of polymorphonuclear (PMN) leukocytes (PMN chemiluminescence) and malondialdehyde (MDA), a lipid peroxidation product, in blood were made at induction of anesthesia (T1), before cross clamping of the aorta (T2), after closure of the chest (T3), and 24 hours postoperatively (T4) in 21 patients undergoing aortocoronary bypass surgery. The total OFR-derived chemiluminescence at T1, T2, T3, and T4 was 1590 ± 156, 3169 ± 338, 1972 ± 214, and 2614 ± 366 mv·min·106 PMN−1, respectively. Superoxide dismutase (SOD)-inhibitable chemiluminescence at T1, T2, T3, and T4 was 1214 ± 129, 2674 ± 328, 1752 ± 215, and 2139 ± 292 mv·min·106 PMN−1, respectively. Superoxide anion at T1, T2, T3, and T4 was 0.99 ± 0.14, 1.30 ± 0.17, 1.07 ± 0.14, and 1.19 ± 0.12 nmol·106 PMN−1·30 min−1, respectively. Blood MDA at T1, T2, T3, and T4 was 0.17 ± 0.02, 0.25 ± 0.03, 0.20 ± 0.03, and 0.23 ± 0.02 nmol/ml, respectively. OFR-derived and SOD inhibitable chemiluminescence, superoxide anion, and blood MDA increased significantly during CPB and postoperatively. There were decreases in the blood pressure and stroke volume, and increases in the central venous pressure, capillary wedge pressure, and heart rate during CPB and postoperatively. Cardiac output remained unchanged during this procedure. There was leukopenia during CPB. The hematocrit and hemoglobin content of blood decreased during bypass and remained low postoperatively. These results suggest that an increase in the level of oxygen free radicals in patients on cardiopulmonary bypass undergoing aortocoronary bypass surgery and 24 hours postoperatively was associated with depressed cardiac function. The increased levels of OFR might be responsible for myocardial dysfunction after cardiopulmonary bypass.

Reaction Dynamics of Electronically Excited Calcium Atom

Absolute values of the total chemiluminescence cross-section for the beam-gas Ca(3P, 1D) + Cl4C → CaCl(A, B) + Cl3C and Ca(3P, 1D) + SF6 → CaF(A, B) + SF5 reactions have been measured at low collision energy, ET = 0.15 and 0.14eV, respectively. Both metastable atomic calcium states Ca(3P, 1D) were produced under low voltage dc-discharge conditions. By changing the discharge conditions, different metastable concentrations were produced to measure the state-to-state cross-section for both 3P and 1D reactions. The following values for the total chemiluminescence cross-sections were obtained:σD1 = 1.77 Å and σP3 = 0.25 Å for the Ca(3P, 1D) + Cl4C → CaCl(A, B) + Cl3C reaction.σD1 = 0.59 Å2 and σP3 = 0.56 Å2 for the Ca(3P, 1D) + SF6 → CaF(A) + SF5 reaction.σD1 = 0.04 Å2 and σP3 = 0.12 Å for the Ca(3P, 1D) + SF6 → CaF(B) + SF5 reaction.In addition, beam-beam experiments were carried out at the same average low collision energy that of the beam-gas, and therefore, normalization between both experiments was possible. This procedure allowed us to obtain the excitation function of the Ca(1D) + SF6 reaction in absolute values over the 0.15–0.60eV collision energy range.On the other hand, by simulation, the ratio of CaCl(B-X/A-X) emissions intensities was found to be of 0.15. The variation of this ratio with the relative concentration of 1D/3P in a Broida oven leads to the conclusion that this state favours the formation of the B state in the chemiluminescent Ca(3P, 1D) + CH3CHCl2 → CaCl(A, B) + CH3CHCl reaction.

A method for the accurate measurement of opsonic activity in uterine secretions of the mare

This study was undertaken to develop a method for accurately measuring opsonic activity in the uterine secretions of the mare. Ten mares were used in the study. They ranged in ages from 6 to 19 years and were of various genital health status. Undiluted uterine secretions were collected by inserting a tampon into the uterus during estrus; serum samples were collected simultaneously Opsonic activity in the secretions and serum was analyzed in a chemiluminescence assay, in which zymosan particles were opsonized. Opsonic activity was determined as peak chemiluminescence, time to peak chemiluminescence, and total chemiluminescence (area under curve). The peak chemiluminescence was 16 to 17 times higher when uterine secretions were used for opsonization rather than when buffer was used. Compared to the opsonic activity in serum, the peak chemiluminescence was 21% (P≤0.05) lower, the time to peak chemiluminescence was 117% (P≤0.05) longer, and the total chemiluminescence over 60 minutes was 7% (P≤0.05) greater in the uterine secretions. These data show that opsonic activity in the uterus is approximately of the same magnitude as that in the circulation.

Hydroperoxide formation in the early stages of polypropylene photo-oxidation

The total chemiluminescence from polypropylene films heated in an inert atmosphere is a sensitive measure of the hydroperoxide content in the induction period of photo-oxidation. The examination of the hydroperoxide content in unstabilised film melt-pressed from the powder, stabilised melt-pressed film and a commercial stabilised film all show a very rapid increase in the hydroperoxide content in the early stages of photo-oxidation which could not be detected by ATR-IR or XPS analysis. This appears as a peak in all of the films which increases in area with film thickness, indicating that it is a bulk property. While stabilisers may inhibit the photo-oxidation as measured by carbonyl index, they cannot prevent this early buildup and decay of hydroperoxides. These are believed to form by the rapid oxidation of the polypropylene in localised zones of high photoinstability. The peak in hydroperoxide content is a consequence of the kinetics of the consecutive reaction of hydroperoxide formation and photolysis which leads to secondary oxidation products and subsequent slower photo-oxidation.

Priming effect of fibronectin on respiratory burst of human neutrophils induced by formyl peptides and platelet-activating factor

Fibronectin (FN), a glycoprotein present in the plasma and the extracellular matrix, has been shown to enhance adherence-related functions of polymorphonuclear leukocytes (PMNs). In this study we investigated the effects of FN on the activation of human PMNs in suspension by soluble stimuli, as determined by the generation of superoxide radicals (respiratory burst). FN (up to 100 micrograms/ml) did not directly stimulate the PMN respiratory burst assessed using a sensitive assay, luminol-dependent chemiluminescence (CL). Low FN concentrations (Up to 25 micrograms/ml) caused a dose-dependent enhancement of the CL induced by two chemoattractants. N-formyl-methionyl-leucyl-phenylalanine (FMLP) and platelet-activating factor (Paf), and also by phorbol myristate acetate (PMA), a known protein kinase C activator. Higher FN concentrations were less effective. The potentiation involved both initial rate and total CL responses and was more active on extracellular than intracellular generation of oxygen radicals. FN potentiation persisted after cell washing and was abolished by treatment of FN with trypsin. Measurement of the respiratory burst using the cytochrome c reduction assay confirmed that FN enhanced both the initial rate and total amount of superoxide anion generated by FMLP-stimulated PMNs. These data indicate that FN facilitates the respiratory burst of chemoattractant-stimulated PMNs and suggest that FN can prepare PMNs in suspension for amplified biological functions induced by soluble inflammatory stimuli.

Reaction dynamics of electronically excited calcium atoms with carbon tetrachloride

Absolute values of the total chemiluminescence cross-section for the beam gas Ca*( 3P, 1D)+Cl 4C→CaCl(A, B)+Cl 3C reaction have been measured at low collision energy, E T=0.15 eV. Both metastable calcium atomic states Ca( 3P, 1D) were produced by low voltage dc-discharge conditions. By changing the discharge conditions different metastable concentrations were produced to measure the state-to-state cross-section for both 3P and 1D reactions. The following values of the total chemiluminescence reaction cross-sections for Ca*( 3P, 1D)+Cl 4C→CaCl*(A, B)+Cl 3C were obtained: σ 1D =1.77 Å 2 and σ 3P =0.25 Å 2.

Reaction Dynamics of Translationaland Electronic Excitation In Ca + SF6Collisions

Relative values of the total chemiluminescence cross.section for the crossed molecular beam urn:x-wiley:02786273:media:lc023523:lc023523-math-0001 reaction have been measured as a function of collision energy. Both metastable calcium atom states 3P1 were produced by low voltage de‐discharge while translational excitation of the SF6 beam was achieved via the seeding technique. Whereas chemiluminescence yield from the urn:x-wiley:02786273:media:lc023523:lc023523-math-0002 was observed from both of the metastable atom reactions, no chemiluminescence signal was detected from the ground atom reaction even though enough translational excitation was used to produc.e that excited product. By changing the discharge conditions different metastable concentrations were produced to measure the state‐to‐state cross‐section for both 3P and 1D reactions, as a function of collision energy, up to 0.6 eV. Laser induced fluorescence of the atomic 4s5s 3S1 ← 4s4p(J = 0, 1, 2, 3) lines have been measured to account for the metastable population in the J = 1 level.