Excitation of eosin when catalyzing electron transport in biochemical systems.

Phenols may participate in electron transport and, as such, catalyze the oxidation of NADH and of acetoacetate in the horseradish peroxidase/Mn²⁺/O₂ system. Eosin can be substituted for the phenol and, in this case, photon emission is observed. The spectrum is mainly eosin fluorescence in the case of NADH oxidation, whereas fluorescence and another emission—presumably phosphorescence—are observed during acetoacetate oxidation. This appears to be the first report of excitation of an electron carrier in biochemical systems.     

Luminescence and energy transfer in Ce3+, Mn2+‐doped K2AEP2O7 (AE = Ca,Sr) phosphor

Pyrophosphates K₂AEP₂O₇ (AE = Ca, Sr) prepared by the classical solid‐state technique and activated with Ce³⁺ are described. Intense emission was observed in K₂AEP₂O₇ (AE = Ca, Sr). The effect of Mn²⁺ co‐doping was studied. The broad emission peak of Mn²⁺ was observed at 534 nm in K₂SrP₂O₇:Ce³⁺ and at 539 nm in K₂CaP₂O₇:Ce³⁺, Mn²⁺. Mn²⁺ emission was greatly enhanced by addition of the sensitizer Ce³⁺ due to efficient energy transfer from Ce³⁺ to Mn²⁺. Copyright © 2015 John Wiley & Sons, Ltd.     

Study on the preparation and luminescence properties of SrGe4O9:Mn4+ red phosphors for plant illumination

In this study, SrGe₄O₉:Mn⁴⁺ red phosphors for plant illumination were prepared using a high-temperature solid-phase method. The samples were characterized and analyzed by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), fluorescence spectroscopy, and other techniques. The phase structure, apparent morphology, and luminescence properties of the SrGe₄O₉:Mn⁴⁺ red phosphors were investigated. The results indicated that the dopant Mn⁴⁺ was incorporated into the matrix structure by substituting some Ge⁴⁺ ions without any changes in the crystal structure of the SrGe₄O₉ matrix. The samples comprised micron-scale particles and exhibited high purity and uniform distribution of elements. The SrGe₄O₉:Mn⁴⁺ phosphors exhibited relatively strong red light emission at 660 nm under the excitation of a 430-nm blue light, and the luminescence intensity was the highest when the Mn⁴⁺ doping amount was 1%. Proper doping of Ti⁴⁺ or Sn⁴⁺ could effectively improve the luminescence intensity of the SrGe₄O₉:Mn⁴⁺ phosphors. The light-emitting diode (LED) device packaging showed that the SrGe₄O₉:Mn⁴⁺ red phosphors could be used for plant growth illumination.     

Peroxidase activity in human red cell: a biological model for excited state molecules generation.

The presence of enzymically generated triplet acetone in red cells and energy transfer to eosin, rose bengal and 9,10-dibromoanthracene-2-sulfonate was indicate by: (1) product distribution; (2) K_ET τ_o, similar to the 2-methylpropanal/peroxidase/O₂ system; (3) correlation between hemolysis, oxygen uptake and photon emission; (4) membrane protection by energy acceptors, and (5) by comparison of the 2-methylpropanal/peroxidase/O₂ system with 2-methylpropanal/red cells/membranes/O₂ and 2-methylpropanal/acid extractable protein from red cells membrane/O₂ systems, which have a high peroxidase activity.This is the first report of a biological system producing a photohemolysis effect in the dark.     

Intense green light emission in Sr2ZnGe2O7:Mn2+ phosphors by the design of high symmetry melilite structure

A green phosphor Sr₂ZnGe₂O₇:Mn²⁺ with a melilite structure was prepared using a high-temperature solid-state reaction. When the 535 nm emission was monitored, the excitation spectrum of the Sr₂ZnGe₂O₇:Mn²⁺ was found to contain two excitation bands in the ultraviolet (UV) region. When excited by UV light, the sample shows bright green emission at 535 nm, which corresponds to the distinctive transition of Mn²⁺ (⁴T₁→⁶A₁). Moreover, the quantum efficiency of Sr₂ZnGe₂O₇:Mn²⁺ could reach 67.6%. Finally, a high-performance white-light-emitting diode (WLED) with a low correlated colour temperature of 4632 K and a high colour rendering index (CRI) of 92.3 were packaged by coating commercial blue and red phosphors with an optimized Sr₂ZnGe₂O₇:Mn²⁺ sample on a 310 nm UV chip. This indicated that Sr₂ZnGe₂O₇:Mn²⁺ has the potential application as a green component in the WLED lighting field.     

Co‐precipitation synthesis and luminescence properties of K2TiF6:Mn4+ red phosphors for warm white light‐emitting diodes

K₂TiF₆:Mn⁴⁺ red phosphors with different Mn⁴⁺ doping concentrations were obtained using the co‐precipitation method. X‐Ray diffraction, scanning electron microscopy, Raman spectra, Fourier transform infrared spectroscopy, photoluminescence excitation and emission spectra and decay curves were used to characterize the properties of K₂TiF₆:Mn⁴⁺ phosphors. Under excitation at 470 nm, an intense red emission peak around 631 nm corresponding to the ²E_g–⁴A₂ transition of Mn⁴⁺ was observed for 2.48 mol% K₂TiF₆:Mn⁴⁺ phosphors and was used as the optimum doping concentration. The excellent luminescent properties of K₂TiF₆:Mn⁴⁺ suggest that this material might be a promising red phosphor for generating warm white light in phosphor‐converted white light‐emitting diodes. Copyright © 2015 John Wiley & Sons, Ltd.     

Dynamics of enzymes generating hydrogen peroxide in solid-state fermentation ofPanus tigrinus on wheat straw

The relationship between the production of extracellular H₂O₂, hydrogen peroxide-producing enzymes and ligninolytic peroxidase was examined during solid-state cultivation ofPanus tigrinus on wheat straw. Glyoxal oxidase, Mn²⁺-dependent peroxidase and glucose oxidase, capable of H₂O₂ generation, were found in the extracellular enzyme preparation. The production of H₂O₂ has two maxima: the maximal production correlates well with the maximal activities of glyoxal oxidase and Mn²⁺-dependent peroxidase, while another, lower peak of H₂O₂ generation is related to the second peak of Mn²⁺-dependent peroxidase activity. The contribution of glucose oxidase to the production of hydrogen peroxide is probably only marginal. Comparison of the dynamics of these extracellular activities and the ligninolytic peroxidase showed good temporal correlation indicating an interrelation of the two processes.     

Effect of Mn2+ and Ca2+ on O2 evolution and on the variable fluorescence yield associated with Photosystem II in preparations of Anacystis nidulans

Extraction with EDTA of lyophilized and lysozyme treated preparations of the blue-green algae Anacystis nidulans resulted in loss of the capacity for photoevolution of O₂. Reactivation was achieved by the addition of both cations: Mn²⁺ and Ca²⁺ (or to a smaller extent by Mn²⁺ and Sr²⁺). The dual requirement for Mn²⁺ and Ca²⁺ could be demonstrated when the O₂ evolution under short saturating light flashes and the variable chlorophyll fluorescence associated with the reduction of the primary acceptor of Photosystem II was examined. The fluorescence experiments in addition showed that incorporation of the cations was a light dependent step, since the fluorescence rise only started after a lag period.     

The structure and luminescence properties of Mn2+/Eu2+/Er3+‐doped MgO‐Ga2O3‐SiO2 glasses and glass‐ceramics

The MgO–Ga₂O₃–SiO₂ glasses and glass‐ceramics samples doped with Eu²⁺/Mn²⁺/Er³⁺ and heated in reductive atmosphere were prepared by the sol–gel method. The structure, morphology and the luminescence properties were studied using X‐ray diffraction, high‐resolution transmission electron microscope, fluorescence spectra, and up‐conversion emission. The luminescence characteristics of doped ions could be influenced by temperature and matrix component. The characteristic emission of Mn²⁺, Eu²⁺ and Er³⁺ were seen and the energy transfer efficiency from Eu²⁺ to Mn²⁺ was enhanced as Mn²⁺ concentration was increased. In addition, the two‐photon process was determined for the Er³⁺‐doped samples.     

Lignin synthesis: The generation of hydrogen peroxide and superoxide by horseradish peroxidase and its stimulation by manganese (II) and phenols

The enzyme horseradish peroxidase (EC 1.11.1.7) catalyses oxidation of NADH. NADH oxidation is prevented by addition of the enzyme superoxide dismutase (EC 1.15.1.1) to the reaction mixture before adding peroxidase but addition of dismutase after peroxidase has little inhibitory effect. Catalase (EC 1.11.1.6) inhibits peroxidase-catalysed NADH oxidation when added at any time during the reaction. Apparently the peroxidase uses hydrogen peroxide (H₂O₂) generated by non-enzymic breakdown of NADH to catalyse oxidation of NADH to a free-radical, NAD., which reduces oxygen to the superoxide free-radical ion, O₂ ^.-. Some of the O₂ ^.- reacts with peroxidase to give peroxidase compound III, which is catalytically inactive in NADH oxidation. The remaining O₂ ^.- undergoes dismutation to O₂ and H₂O₂. O₂ ^.- does not react with NADH at significant rates. Mn²⁺ or lactate dehydrogenase stimulate NADH oxidation by peroxidase because they mediate a reaction between O₂ ^.- and NADH. 2,4-Dichlorophenol, p-cresol and 4-hydroxycinnamic acid stimulate NADH oxidation by peroxidase, probably by breaking down compound III and so increasing the amount of active peroxidase in the reaction mixture. Oxidation in the presence of these phenols is greatly increased by adding H₂O₂. The rate of NADH oxidation by peroxidase is greatest in the presence of both Mn²⁺ and those phenols which interact with compound III. Both O₂ ^.- and H₂O₂ are involved in this oxidation, which plays an important role in lignin synthesis.     

Emission analysis of Tb3+‐and Sm3+‐ion‐doped (Li2O/Na2O/K2O) and (Li2O + Na2O/Li2O + K2O/K2O + Na2O)‐modified borosilicate glasses

Four series of borosilicate glasses modified by alkali oxides and doped with Tb³⁺ and Sm³⁺ ions were prepared using the conventional melt quenching technique, with the chemical composition 74.5B₂O₃ + 10SiO₂ + 5MgO + R + 0.5(Tb₂O₃/Sm₂O₃) [where R = 10(Li₂O /Na₂O/K₂O) for series A and C, and R = 5(Li₂O + Na₂O/Li₂O + K₂O/K₂O + Na₂O) for series B and D]. The X‐ray diffraction (XRD) patterns of all the prepared glasses indicate their amorphous nature. The spectroscopic properties of the prepared glasses were studied by optical absorption analysis, photoluminescence excitation (PLE) and photoluminescence (PL) analysis. A green emission corresponding to the ⁵D₄ → ⁷F₅ (543 nm) transition of the Tb³⁺ ions was registered under excitation at 379 nm for series A and B glasses. The emission spectra of the Sm³⁺ ions with the series C and D glasses showed strong reddish‐orange emission at 600 nm (⁴G_5/2 →⁶H_7/2) with an excitation wavelength λ_exci = 404 nm (⁶H_5/2→⁴F_7/2). Furthermore, the change in the luminescence intensity with the addition of an alkali oxide and combinations of these alkali oxides to borosilicate glasses doped with Tb³⁺ and Sm³⁺ ions was studied to optimize the potential alkali‐oxide‐modified borosilicate glass.     

A stopped‐flow study of the dual chemiluminescence for the luminol–KIO4–Mn2+ system in strong alkaline solutions

A novel phenomenon of dual chemiluminescence (CL) was observed for the KIO₄–luminol–Mn²⁺ system in strong alkaline solutions using the stopped‐flow technique. Scavenging study of the reactive oxygen species (ROS) suggested that the two CL peaks originated from different CL pathways precipated by distinct ROS (O₂^? and ^?OH for the first peak, mainly ¹O₂ for the second peak). Generation of these ROS at different time intervals from the reactions involving IO₄^?, O₂, and Mn²⁺ and their subsequent reactions with luminol induced the intense CL emission. The relative intensity of the two CL peaks can be tuned over a wide range by varying the concentrations of Mn^2?, luminol and KIO₄. Because of the involvement of different ROS in each pathway, the two CL peaks could respond quite differently to various substances. Moreover, variation of the intensity ratio of the two CL peaks altered the relative proportions of the corresponding ROS, thereby changing their responses to a given substance. The dual CL emission acts like a pair of tunable probes and it is believed that this CL system has great potential in analytical applications. Copyright © 2010 John Wiley & Sons, Ltd.     

Combined effects of hypoxia and excess Mn2+ on oxidative stress and antioxidant enzymes in tomato seedlings

Effects of high level of Mn²⁺ on the changes in ROS generation, root cell viability, antioxidant enzyme activities, and related gene expression in tomato (Solanum lycopersicum L., cv. Zhongza 9) seedlings were studied under normoxic and hypoxia conditions. Mn²⁺ concentrations, ranged between 10 and 200 ??M, led to significantly higher activities of superoxide dismutase (SOD), peroxidase (POD), ascorbate peroxidase (APOD), glutathione reductase (GR), and also ascorbic acid (AsA) content in leaves and roots, improved root cell viability, and decreased O ₂ ^·? accumulation compared with the higher Mn²⁺ level under hypoxia stress, which indicated that low Mn²⁺ could eliminate the active oxygen and protect the membrane lipid from the hypoxia hurt. When the concentration of Mn²⁺ reached 400?C600 ??M under hypoxia stress, the activities of SOD, POD, APOD, and GR and AsA content were decreased remarkably. In contrast, the MDA content was increased at the higher Mn²⁺ concentration. A number of antioxidant-related genes showed high expression at the lower level of Mn²⁺. The expression levels of SOD, POD, CAT, APOD, and GR genes were 7.95, 5.27, 3.18, 5.54, and 8.81 times compared to control, respectively. These results illustrated that the appropriate amount of Mn²⁺ could alleviate the detrimental effects of hypoxia stress, but reversely, the high level of Mn²⁺ just aggravated the existing damage to the tomato seedlings.     

Structural and photoluminescence study of Mn2+‐activated CaYAl3O7 blue phosphors

The structural and photoluminescence properties of CaYAl₃O₇ phosphor material doped with varying concentration of Mn²⁺ have been studied. The phosphor material was synthesized by the combustion method at 500 °C and was characterized using X‐ray diffraction, Fourier transform infrared spectroscopy and photoluminescence spectroscopy (PL). X‐ray diffraction showed that the crystallites have average sizes in the range of ~58–70 nm. Corresponding Fourier transform infrared spectroscopy investigations confirm the phase formation and the presence of aluminate group (Al‐O bands) in CaYAl₃O₇:Mn²⁺ phosphor. Under the excitation at 356 nm wavelength, the PL spectra show the occurrence of two emission peaks obtained in the blue region at 389 nm and 412 nm, which is attributed to the 4 T1(G) → 6A1 transition of Mn²⁺ ion. Upon increasing Mn²⁺ concentration, the relative PL intensity shows an initial decrement followed by an increase displaying the effect of concentration quenching. Overall the results suggest the possibility of using this material in white lighting devices and plasma display panels. Copyright © 2013 John Wiley & Sons, Ltd.     

Light emission from the Fe2+–EDTA–ascorbic acid–H2O2 system strongly enhanced by plant phenolic acids

Oxidative reactions can result in the formation of electronically excited species that undergo radiative decay depending on electronic transition from the excited state to the ground state with subsequent ultra‐weak photon emission (UPE). We investigated the UPE from the Fe²⁺–EDTA (ethylenediaminetetraacetic acid)–AA (ascorbic acid)–H₂O₂ (hydrogen peroxide) system with a multitube luminometer (Peltier‐cooled photon counter, spectral range 380–630 nm). The UPE, of 92.6 μmol/L Fe²⁺, 185.2 μmol/L EDTA, 472 μmol/L AA, 2.6 mmol/L H₂O₂, reached 1217 ± 118 relative light units during 2 min measurement and was about two times higher (P < 0.001) than the UPE of incomplete systems (Fe²⁺–AA–H₂O₂, Fe²⁺–EDTA–H₂O₂, AA–H₂O₂) and medium alone. Substitution of Fe²⁺ with Cr²⁺, Co²⁺, Mn²⁺ or Cu²⁺ as well as of EDTA with EGTA (ethylene glycol‐bis(β‐aminoethyl ether)‐N,N,N′,N′‐tetraacetic acid) or citrate powerfully inhibited UPE. Experiments with scavengers of reactive oxygen species (dimethyl sulfoxide, mannitol, sodium azide, superoxide dismutase) revealed the dependence of UPE only on hydroxyl radicals. Dimethyl sulfoxide at the concentration of 0.74 mmol/L inhibited UPE by 79 ± 4%. Plant phenolics (ferulic, chlorogenic and caffec acids) at the concentration of 870 μmol/L strongly enhanced UPE by 5‐, 13.9‐ and 46.8‐times (P < 0.001), respectively. It is suggested that augmentation of UPE from Fe²⁺–EDTA–AA–H₂O₂ system can be applied for detection of these phytochemicals.     

Oxidation of manganous pyrophosphate by superoxide radicals and illuminated spinach chloroplasts.

The oxidation of Mn²⁺-pyrophosphate to Mn³⁺ by superoxide (O₂^?) was quantitative as evidenced from the formation of Mn³⁺-pyrophosphate and hydrogen peroxide and from the inhibition by superoxide dismutase. Using the competitive relation between Mn²⁺-pyrophosphate and superoxide dismutase for the O₂^?, the rate constant of Mn²⁺ oxidation was estimated to be about 6 × 10⁶m^?1 s^?1. The oxidation of Mn²⁺-pyrophosphate by illuminated chloroplasts was also indicated to be stoichiometrically induced by O₂^?. In the presence of saturating amounts of the Mn²⁺, a double enhancement of hydrogen peroxide production and triple uptake of oxygen were found, as expected from the oxidation of Mn²⁺-pyrophosphate by O₂^?. Anaerobiosis or superoxide dismutase annuled these increments. We propose that the O₂^? generated as the sole initial step of the Mehler reaction oxidized Mn²⁺-pyrophosphate, and we discuss the role of free manganese in chloroplasts.     

Luminescence studies on Ba2ZnSi2O7 : Eu2+ phosphors crystals

A novel blue green‐emitting phosphor Ba₂ZnSi₂O₇ : Eu²⁺ was prepared by combustion synthesis method and an efficient bluish green emission under from ultraviolet to visible light was observed. The emission spectrum shows a single intensive band centered at 503 nm, which corresponds to the 4f⁶5d¹ → 4f⁷ transition of Eu²⁺. The excitation spectrum is a broad band extending from 260 to 465 nm, which matches the emission of ultraviolet light‐emitting diodes (UV‐LEDs). The effect of doped Eu²⁺ concentration on the emission intensity of Ba₂ZnSi₂O₇ : Eu²⁺ was also investigated. The result indicates that Ba₂ZnSi₂O₇ : Eu²⁺ can be potentially useful as a UV radiation‐converting phosphor for white light‐emitting diodes. Copyright © 2009 John Wiley & Sons, Ltd.     

Lead-hemoglobin interaction as a possible source of reactive oxygen species—A chemiluminescent study

Pb²⁺-hemoglobin interaction as a possible source of reactive oxygen species was investigated. It was found that the products of this reaction are able to promote peroxidase catalyzed luminol oxidation with light emission. Superoxide dismutase and catalase strongly inhibited this effect. A conclusion was done that the interaction between Pb²⁺ and oxyhemoglobin yields reactive oxygen species, possibly O₂^? and H₂O₂.     

Molten salt synthesis and luminescence of Dy3+‐doped Y3Al5O12 phosphors

Dy³⁺‐doped Y₃Al₅O₁₂ phosphors were prepared at a relatively low temperature using molten salt synthesis. The phase of the prepared Dy³⁺‐doped Y₃Al₅O₁₂ phosphors was confirmed using X‐ray powder diffraction. Results indicated that Dy³⁺ doping did not change the Y₃Al₅O₁₂ phase. Following excitation at 352 nm, emission spectra of the Dy³⁺‐doped Y₃Al₅O₁₂ phosphors consisted of blue, yellow, and red emission bands. The influence of Dy³⁺ concentration and excitation wavelength on emission was investigated. The ratio of yellow light to blue light varied with change in Dy³⁺ doping concentration, due to changes in the structure around Dy³⁺. Emission intensities also changed when the excitation wavelength was changed. This variation is luminescence generated a system for tunable white light for Dy³⁺‐doped Y₃Al₅O₁₂ phosphors.     

A novel Mn4+-activated far-red Sr2MgWO6 phosphor: synthesis,luminescence enhancement,and application prospect

A novel far-red emitting phosphor Sr₂MgWO₆: Mn⁴⁺ was fabricated using high-temperature solid-state reaction. X-ray diffraction patterns, scanning electron microscopy images, and photoluminescence excitation and photoluminescence spectra for this phosphor were analyzed in detail. The analysis revealed that its emission ranged from 600 to 800 nm and peaked at 699 nm, which was attributed to the ²E_g→⁴A_2g transition of Mn⁴⁺ under 314 nm excitation. Moreover, we introduced rare-earth Yb³⁺ ions into the Sr₂MgWO₆:Mn⁴⁺ to improve its far-red emitting intensity. The photoluminescence (PL) intensity of the Yb³⁺ co-doped phosphor was three times higher than that of the single-doped phosphor. Therefore charge compensation is an efficient approach to improving PL intensity. The phosphor emitted a far-red light that resembled the pigments essential for plant growth in terms of the absorption spectrum. Therefore, the obtained phosphor, Sr₂MgWO₆:0.006Mn⁴⁺,0.2Yb³⁺, had the potential to be a new type of far-red luminescent powder for indoor plant growth LEDs.