THE 75°C THERMOLUMINESCENCE BAND OF GREEN TISSUES: CHEMILUMINESCENCE FROM MEMBRANE-CHLOROPHYLL INTERACTION

Abstract— Exposure of thylakoid membranes of green plants to high temperature promotes the appearance of free radicals resulting in a thermoluminesccnce (TL) band peaking around 75°C. The occurrence of this band with the same intensity in prcilluminated and in dark-adapted samples demonstrates that, contrary to several other TL bands, it is not a result of charge recombination. The high temperature TL band is oxygen dependent. Parallel to TL emission singlet oxygen is formed, as demonstrated by spin trapping EPR measurements and by the decrease of TL intensity in the presencc of sodium-azide, a singlet oxygen scavenger.
We suggest that the 75°C TL band is a result of a temperature-enhanced interaction between molecular oxygen and the photosynthetic membrane, possibly involving lipid peroxidation. The spectral maximum of the emission (around 720 nm) implics that light emission occurs upon energy transfer from an excited product to chlorophyll molecules destablized from pigment-protein complexes.     

Tunable photoluminescent and cathodoluminescent properties of ZnO and ZnO:Zn phosphors

ZnO and ZnO:Zn powder phosphors were prepared by the polyol-method followed by annealing in air and reducing gas, respectively. The samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), X-ray photoelectron spectra (XPS), electron paramagnetic resonance (EPR), and photoluminescence (PL) and cathodoluminescence (CL) spectra, respectively. The results indicate that all samples are in agreement with the hexagonal structure of the ZnO phase and the particle sizes are in the range of 1-2 microm. The PL and CL spectra of ZnO powders annealed at 950 degrees C in air consist of a weak ultraviolet emission band (approximately 390 nm) and a broad emission band centered at about 527 nm, exhibiting yellow emission color to the naked eyes. When the sample was reduced at the temperatures from 500 to 1050 degrees C, the yellow emission decreased gradually and disappeared completely at 800 degrees C, whereas the ultraviolet emission band became the strongest. Above this temperature, the green emission ( approximately 500 nm) appeared and increased with increasing of reducing temperatures. According to the EPR results and spectral analysis, the yellow and green emissions may arise from the transitions of photogenerated electron close to the conduction band to the deeply trapped hole in the single negatively charged interstitial oxygen ion (Oi(-)) and the single ionized oxygen vacancy (V.O) centers, respectively.     

EFFECT OF INACTIVATION OF THE OXYGEN-EVOLVING SYSTEM ON THE THERMOLUMINESCENCE OF ISOLATED CHLOROPLASTS

Abstract— The effect of inactivation of water-splitting enzyme on the thermoluminescence of isolated chloroplasts was investigated. The inhibitory treatments used included Tris-washing, alkaline pH in the presence of the uncoupler gramicidin, incubation with a high concentration of magnesium ions and different chaotropic agents. It was found that inhibition of oxygen evolution resulted in the disappearance of the main thermoluminescence band at +20°C. The A band which appears at — 10°C and has been related to the S₄ state of the water-splitting enzyme (Inoue, 1981) was not considerably affected by the inhibition of oxygen evolution. The results presented here indicate that the participation of the S₄ state of water-splitting enzyme in the generation of the A band should be reinvestigated.     

Photoelectron emission and XPS studies of real iron surfaces subjected to scratching in air,water, and organic liquids

The influence of temperature and surface overlayer on the photoelectron emission from scratched real iron surfaces was investigated using thermally assisted photoelectron emission (TAPE) and X‐ray photoelectron spectroscopy (XPS) measurements. The scratching was conducted with a diamond cutter in seven atmospheres. The intensity of TAPE as a function of temperature, called glow curve, was measured in the range 25–339 °C using a Geiger counter under ultraviolet irradiation at 210 nm. The temperature was scanned in two cycles (Up1 and Down1, and Up2 and Down2). The XPS measurements were carried out at 25 °C and after TAPE measurements at 200 and 339 °C. The photoelectron emission intensity at 40 °C in the Up1 scan increased in the order of air < water ≈ methanol ≈ cyclohexane < ethanol < benzene < acetone, and then each glow curve exhibited a gradual increase with temperature through a broad peak. It was found that the dependence of the emission intensity in the Up1 scan on the oxygen component ratio, Z_O = O^2?/(OH^? + O^2?) and the percentage of the Fe metal and FeOOH components of the Fe3p spectra for the atmospheres greatly differed. Additionally, the glow curve in the Up1 scan was completely different from that in the other scans. It was proposed that the photoelectron emission in the Up1 scan originates from not only the base metal but also the surface overlayer having trapped electrons and is strongly influenced by the acid–base interaction of the surface hydroxyl groups with the liquids molecules. Copyright © 2016 John Wiley & Sons, Ltd.     

共掺Tm~(3+)离子对CaAlSiN_3∶Eu~(2+)红色荧光粉发光性能的影响

通过高温固相法,合成了Eu~(2+)单掺和Eu~(2+)、Tm~(3+)共掺CaAlSiN_3荧光粉。结合荧光光谱、余辉发射光谱和余辉衰减曲线及热释发光等测试手段对其进行了表征分析。结果表明,CaAlSiN_3∶Eu~(2+)具有主峰位于630 nm的明显的红色长余辉发光;共掺杂Tm~(3+)离子的引入,产生了654和800 nm的荧光和余辉,同时,Tm~(3+)的共掺,使CaAlSiN_3∶0.1%Eu~(2+),Tm~(3+)样品位于89.0℃热释光峰位消失,表明Tm~(3+)共掺杂改变了CaAlSiN_3∶Eu~(2+)荧光粉中的陷阱能级及其分布,从而减弱了CaAlSiN_3∶Eu~(2+)的630 nm红色可见光部分余辉发光性能。     

Detection of CN radicals in DC nitrogen plasma used for deposition of CNx layers

Emission spectra from a DC plasma discharge of nitrogen with a graphite cathode used for deposition of CNx layers were investigated in the visible range 350-900 nm. The spectra recorded at low and high resolution from both the negative glow and the positive column of the discharge were studied separately. All spectra are dominated by neutral and ionised N2 emission. In the positive column the violet band of the cyanogen (CN) radical was identified and analysed for vibrational structure. From a computer simulation of the rotationally resolved violet band, vibrational temperatures were derived and found to be in the intensity distribution for the nu = 0, 1 and 2 levels from thermal equilibrium. In the negative glow the strong N2+ features completely mask the spectral region of the violet band of CN. Conclusions were drawn concerning the CN formation by chemical sputtering, and the role of CN radicals in the formation of polymeric CNx layers of 1:1 = C:N stoichiometry.     

Chemiluminescence study on the oxidation of several polyolefins—I. Thermal-induced degradation of additive-free polyolefins

Chemiluminescence (CL) has been applied to evaluate the oxidation susceptibility of various polyolefins: low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE) and isotactic polypropylene (i-PP). The intensity of CL emission in inert atmosphere could be related to the previous oxidation level. The thermal stability at 170 °C of the hydroperoxides in LDPE seems to be lower than that in LLDPE or HDPE. The kinetic parameters of the oxidation at 170 °C in oxygen, calculated from CL data, suggest the following stability order: HDPE > LLDPE > LDPEi-PP. The intensity of CL emission was related to the CH₃ content as evaluated by Fourier transform infra-red spectroscopy.     

Transformation of the Photoacoustic Signal after Treatment of Barley Leaves with Methylviologen or High Temperatures

Abstract— The photoacoustic (PA) signal at the modulation frequency of 35 Hz was studied in MV-treated barley leaves or leaves preheated at different temperatures. Saturating illumination enhanced the magnitude of the PA signal in MV-treated leaves in contrast with the opposite result usually found in untreated intact leaves where saturating illumination abolishes the photobaric component of the PA signal due to oxygen evolution and thus decreases the total PA signal. A linear relationship was found between the changes induced by continuous background light in the negative response of PA signal to saturating light in intact leaves and in the positive response in MV-treated leaves. A linear relationship was also observed in MV-treated leaves between the positive changes in the PA signal and the changes in the rate of electron transport through photosystem II (PSII) calculated from chlorophyll fluorescence data. The conclusion was drawn that only the thermal component contributes to the PA signal measured at low modulated frequency in MV-treated leaves because the enhanced O2 uptake provides a zero net oxygen exchange by superimposing with O2 evolution. The leaves preheated at temperatures above 43°C demonstrated the positive response of the PA signal to saturating light at 35 Hz. In leaves preheated at 41.5°C, the first and second saturating pulses induced the enhancement of PA signal, whereas other pulses decreased the PA signal due to onset of oxygen evolution. The energy storage activity measured in the absence of oxygen evolution in heat-treated leaves is proposed to be associated with cyclic electron transport activities around PSII and PSI.     

Rare earth complexes chemiluminescence catalyzed by gold nanoparticles for fast sensing of Tb3+ and Eu3+

Developing multiplex sensing technique is of great significance for fast sample analysis. However, the broad emissions of most chemiluminescence(CL) luminophores make the multiplex CL analysis be difficult. In this work, a simple and sensitive CL analytical method has been developed for the simultaneous determination of Tb³⁺and Eu³⁺thanking to their narrow band emission. The technique was based on a mixed CL system of periodate(IO₄^-)-hydrogen peroxide(...     

Alkaline phosphatase-labeled macromolecular probe for sensitive chemiluminescence detection of proteins on a solid-phase membrane

In the present study, we synthesized dextran (MW = ca. 2,000 kDa)-based macromolecular probes containing multiple molecules of alkaline phosphatase (ALP) as a signal-trigger enzyme and of biotin as an assembly mediator. The ALP and biotin molecules were covalently attached into the dextran backbone after the formation of aldehyde groups into the macromolecule by periodate oxidation. The synthesized probes contained 27–31 molecules of ALP in their macromolecules when 50-fold molar ratio of ALP to the dextran was used for the synthesis. These probes provided 14–20 times stronger chemiluminescence (CL) than that of the equimolar free ALP adsorbed on a nylon membrane. The velocity of the CL reaction of ALP-catalyzed adamantlyl-1,2-dioxetane substrate was improved from a slower emission (glow type) of CL to a faster one (flash type). The CL signal integrated for 2 min under strongly alkaline conditions (pH 13.0) was about ten times greater than that obtained by the conventional conditions (pH 9.5). Therefore, the synthesized macromolecular probe could be successfully utilized for the high-throughput CL detection of biotin-conjugated anti-rabbit IgG antibody with a lower detection limit of 880 amol per spot on the nylon membrane. This study provides analytical strategy for the rapid, convenient, and sensitive detection of target proteins in immunoassays.     

THERMALLY STIMULATED LUMINESCENCE OF UV-AND X-IRRADIATED CAFFEINE

Abstract— Thermally stimulated luminescence studies of UV- and X-irradiated caffeine have been conducted in the interval77–300 K. The X-ray-induced glow curve exhibits peaks at 102, 128, 158, and 198 K, whereas the UV-induced curve is characterized by peaks with maxima at 120 and 208 K. Analysis of the X-ray-induced glow peaks revealed that the 102 and 128 K peaks obeyed first-order kinetics, while the 158 and 198 K ones followed orders of 1.3 and 1.8, respectively. Trapping parameters associated with the peaks were also elucidated. Concomitant emission spectra of each glow peak (both UV and X-ray induced) were identical and consisted of a band with well-defined maxima at 405 and 480 nm which are attributed to singlet (S₁→ S₀+ h v ) and triplet (T₁→ S₀+ h v ) transitions, respectively. At elevated temperatures the triplet transition is not observed due to quenching of the triplet state or to triplet-triplet interactions. An energy-level diagram depicting the thermally stimulated processes in irradiated caffeine is presented.     

STRUCTURAL STUDIES OF BROWN MEMBRANE BY X-RAY DIFFRACTION, CIRCULAR DICHROISM AND ABSORPTION SPECTRA

Abstract— Time course of formation and crystallization of bacteriorhodopsin upon the addition of retinal to brown apo-membrane has been studied by X-ray diffraction, circular dichroism (CD) spectra and absorption spectra. The rate of formation of bacteriorhodopsin decreases markedly at low pH (4.8) and low temperature (5°C). Furthermore, the formation of bacteriorhodopsin does not proceed in fully dried membranes. The half-time of the increase of exciton CD band is about 70s at 17°C and pH 7.0, and is comparable to that of the formation of bacteriorhodopsins (∼48s). The crystallization of bacteriorhodopsin proceeds to a large extent within 30 min at pH 7.0 and 5°C.
The bilobed CD band of the brown holo-membrane attributed to exciton coupling of bacteriorhodopsin molecules becomes negligibly small at pH 4.8, even though X-ray diffraction pattern indicates the lattice structure to be similar to that of the native purple membrane.     

Electronic and vibrational spectra of some rare earth trifluoromethanesulfonates crystals

Nanocrystalline ZnO powders have been synthesized by a low temperature solution combustion method. The photoluminescence (PL) spectrum of as-formed and heat treated ZnO shows strong violet (402, 421, 437, 485 nm) and weak green (520 nm) emission peaks respectively. The PL intensities of defect related emission bands decrease with calcinations temperature indicating the decrease of Zn(i) and V(o)(+) caused by the chemisorptions of oxygen. The results are correlated with the electron paramagnetic resonance (EPR) studies. Thermoluminescence (TL) glow curves of gamma irradiated ZnO nanoparticles exhibit a single broad glow peak at ～343°C. This can be attributed to the recombination of charge carriers released from the surface states associated with oxygen defects, mainly interstitial oxygen ion centers. The trapping parameters of ZnO irradiated with various γ-doses are calculated using peak shape method. It is observed that the glow peak intensity increases with increase of gamma dose without changing glow curve shape. These two characteristic properties such as TL intensity increases with gamma dose and simple glow curve structure is an indication that the synthesized ZnO nanoparticles might be used as good TL dosimeter for high temperature application.     

ROLE OF ELECTRIC POLARIZATION IN THE THERMOLUMINESCENCE OF CHLOROPLASTS

Abstract Effect of an external electric field on thermoluminescence and thermodepolarization currents were studied in suspensions and dry films of pea chloroplasts. The external electric field was applied either during interrupted heating at a given temperature ("direct effect") or was "stored" in the sample during cooling in the range –25°C and –70°C ("electret effect").
It is shown that in chloroplast suspension both the luminescence burst upon "direct effect" and the new band peaking between –40°C and –50°C induced by the "electret effect" are accompanied by a preferential decrease in the intensity of the thermoluminescence band around +10°C.
A correlation was established between the polarized state of thylakoids and the thermoluminescence burst induced by the external field. In electret samples of chloroplast suspension the intensity of field induced low temperature thermoluminescence band under different experimental conditions varied in parallel with the intensity of thermodepolarization current. In dry films of chloroplasts, in addition to parallel changes in intensities of thermoluminescence and thermodepolarization current, also the peak positions shifted in the same manner when either humidity of samples or temperature of illumination and of application of external field were varied.
We conclude that the polarization state of thylakoid membrane, which can be governed by an external electric field, plays an important role in determining charge stabilization and recombination properties of photosynthetic units. Our results implicate that electric field induces conformational changes in the membranes which increases the frequency factor ascribed to the recombination processes.     

激活CaO-MgO-SiO_2长余辉玻璃发光性质

报道了一种新型的Eu~(2+)离子激活硅酸盐玻璃,该玻璃组成为2CaO-MgO-3SiO_2-0.015Eu_2O_3(CMSE)。通过透射光谱、稳态荧光光谱、余辉光谱和热释光等技术手段对CMSE的发光性质进行了深入研究。研究发现CMSE可以被紫光和近紫外光激发,获得黄色长余辉发光。热释光曲线的分析表明,CMSE的长余辉性质主要来自于玻璃基质中陷阱深度为0.83 e V左右的定域能级。研究认为对CMSE发光性质的研究有利于开发新型稀土离子激活近紫外激发LED用硅酸盐玻璃发光材料。     

DEVELOPMENT OF THERMOLUMINESCENCE BANDS DURING GREENING OF WHEAT LEAVES UNDER CONTINUOUS AND INTERMITTENT ILLUMINATION

Abstract— Mature wheat leaves excited by 1-min illumination at a low temperature of -60° C showed five thermoluminescence bands at -45, -10, +25, +40 and +55° C (denoted as Z_u, A, B₁ B₂ and C bands, respectively). The development of these bands during greening of etiolated wheat leaves under continuous and intermittent illumination was investigated, and the following results were obtained. (1) Etiolated leaves showed only the C band. When these leaves were greened under continuous light, the B₁ and B₂ bands appeared at 3 h and the Z_u band appeared at 10 h. The B₁ and B₂ bands were intensified during prolonged greening under continuous illumination to be the strong bands observed for mature leaves. The A band and the group of B₁ and B₂ bands were alternative: Similar experiments by excitation of thermoluminescence at -20° C showed the development of the A band instead of these B₁ and B₁ bands. (2) When the etiolated leaves were greened under intermittent illumination (1-ms light + 5-min dark), the Z_u band first appeared after 5 h of illumination (60 flashes) and was gradually intensified during further illumination with 340 flashes but, interestingly, neither the B₁ nor the B₂ band appeared even after 24–28 h of illumination with 280–340 flashes. (3) On exposure of such leaves greened under intermittent illumination to continuous light, the B₁ and B₂ bands were rapidly developed. The appearance of these bands was accompanied by the generation of the Hill activity (DCIP photoreduction with water as electron donor). (4) These results were discussed in relation to the previous study on photoactivation of the latent water-splitting system accumulated in the leaves greened under intermittent illumination. It was deduced that the structure responsible for the A band or the group of B₁ and B₂ bands is involved in the evolution of oxygen in chloroplasts, and probably involves cations of the Mn²⁺ catalyst generated by the action of light.     

Response calculations of electronic and vibrational transitions in molecular oxygen induced by interaction with noble gases

The Einstein coefficient for the singlet oxygen emission a1Deltag-->X3Sigmag- at lambda=1270 nm and b1Sigmag+-->X3Sigmag- emission at lambda=750 nm were calculated by quadratic response (QR) multiconfiguration self-consisted field (MCSCF) method for a number of collision complexes O2+M, where M=He, Ne, Ar. Interaction with He clusters was studied in order to simulate cooperative effect of the environment on the oxygen emission. Calculations of the dipole transition moment for the Noxon band, b1Sigmag+-a1Deltag, by linear response (LR) MCSCF method were also performed for a number of collision complexes. Spin-orbit coupling (SOC) between the b1Sigmag+ and X3Sigmag- (MS=0) states does not change much upon collisions, thus the a-X transition borrows intensity mostly from the collision-induced Noxon band b-a. The a-X intensity borrowing from the Schumann-Runge transition is negligible. The calculations show that the b-a and a-X transition probabilities are enhanced approximately by 10(5) and 10(3) times by O2+M collisions. An order of magnitude differences occur for both transitions for noble gases with large difference in polarizability. A strong cooperative effect is obtained when few He atoms perturb the oxygen molecule. Depending on mutual orientation of the partners it can be a complete quenching of the a-->X emission or strong non-additive enhancement. Collision-induced infrared vibrational transitions in a number of molecular oxygen excited states were studied and shown to be state selective.     

Comparison of N-alkyl acridine orange dyes as fluorescence probes for the determination of cardiolipin

The phospholipid (PL), cardiolipin (CL), is found almost exclusively in the inner membrane of mitochondria and loss of CL is considered as an important indication of cell apoptosis. Previously, 10-N-nonyl acridine orange (NAO) has been used as a fluorescent probe for the visualization of CL in mitochondrial cell membranes and in solution. In this work for the determination of CL, we have synthesized two new fluorescent probes, n-tetradecyl acridine orange (C14-AO), and n-octadecyl acridine orange (C18-AO) by reacting acridine orange with the corresponding n-alkyl bromide. Using excitation and emission wavelengths at about 500 and 525 nm and varying the percentage of methanol in water as the solvent, no interaction between CL and the fluorescent probes at 75% is noted but a proportional quenching of the fluorescence signal by CL is observed at 50% or less for C14-AO and 60% or less for C18-AO. Binding efficiency of these fluorescent probes to CL is compared using dye concentrations of 5, 10, and 20 μM. C18-AO shows a better sensitivity than C14-AO and NAO, respectively, but is less selective. For C14-AO, the detection limit and limit of quantitation are 0.07 and 0.21 μM, respectively, which are better than those previously reported for NAO. One anionic PL, phosphatidic acid, shows some quenching interference to both the C14 and C18 dyes but only at concentrations above the working range for sample analysis. The CL in mitochondrial membrane samples is determined by standard addition using C14-AO. The level of CL in the outer mitochondrial membrane compared to the inner membrane is significantly increased due to the addition of cadmium chloride into the cells causing cell apoptosis.     

Fluorosurfactant-capped gold nanoparticles-enhanced chemiluminescence from hydrogen peroxide-hydroxide and hydrogen peroxide-bicarbonate in presence of cobalt(II)

Nonionic fluorosurfactant (FSN)-capped gold nanoparticles (GNPs) remain excellently stable at a wider pH range and high ionic strength, which is useful to investigate some CL systems involved in high salt and a strict pH range. In this study, we utilized FSN-capped GNPs of different sizes to distinguish the emitting species from H2O2-Co2+-NaOH and H2O2-Co2+-NaHCO3 systems. When the pH of FSN-capped gold colloidal solution was adjusted to 10.2 by dropwise addition of 0.05 M NaOH, the CL intensity of H2O2-Co2+-NaHCO3 system was enhanced 6-fold or 60-fold respectively in the presence of FSN-capped 14 nm or 69 nm GNPs with comparison to H2O2-Co2+-NaOH. The variation of CL spectra and UV-vis spectra, as well as the quenching effect of reactive oxygen species scavengers were studied in detail to understand the CL enhancement mechanisms of FSN-capped GNPs on the two systems. For H2O2-Co2+-NaOH system, the gold(I) complexes intermediate and singlet oxygen dimol species were proposed as the emitting species. The excited states of the carbon dioxide dimers and singlet oxygen dimol species were considered responsible for the light emission of H2O2-Co2+-NaHCO3 system. To our knowledge, this work is the first time to study the two CL systems simultaneously using nanoparticles.     

Optical properties of sol-gel synthesized calcium doped ZnO nanostructures

Optical properties of Ca doped ZnO nanoparticles prepared at room temperature through wet chemical method have been investigated. X-ray diffraction studies show that particles are crystalline in nature and doping did not induce impurity phases. Optical absorption measurements show an absorption peak at ∼372 nm which is due to excitonic absorption of the ZnO. Photoluminescence studies reveal a broad emission at an excitation wavelength of 335 nm and the bands are attributed to near band edge emission, oxygen vacancies, surface dangling bonds and zinc interstitials. Incorporating Ca²⁺ induces reduction in near band edge emission and there is an enhancement in the oxygen vacancy peaks which are attributed to the shape changes in the nanoparticles.