Photo- and Thermobleaching of Luminescence Centers in Synthetic Opals

It has been found that on exposure of specimens of synthetic opal to UV radiation, luminescence is excited in them (337 nm) that has spectral maxima at 400 and 500 nm. Its duration at half-height of a pulse is 9 nsec, and there is a weak slow component with τ ∼ 1 μsec. The spectrum and intensity of the luminescence depend on the duration of irradiation and temperature. The luminescence bands revealed relate to two individual luminescence centers, namely: the shortwave one, caused by the luminescence centers formed in the bulk of the opal, and the longwave one, due to those formed on the opal surface. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 5, pp. 622–626, September–October, 2005.     

Luminescence of thulium-activated cubic boron nitride

Under high pressure and temperature conditions, we have obtained samples of thulium-activated cubic boron nitride in the form of micropowders, ceramics, and polycrystals activated by thulium in the presence of aluminum. We studied the cathodoluminescence (CL), photoluminescence (PL), and photoluminescence excitation spectra of the samples. In the luminescence spectra we observe structured bands with maxima at ∼370, ∼475, ∼660, and ∼ 800 nm, assigned to electronic transitions in the triply charged thulium ions. We have established that the most efficient method for excitation of “blue” luminescence at ∼475 nm for thulium ions in cBN is excitation by an electron beam. The cBN samples synthesized in the presence of Al have photoluminescence spectra with a more complex structure compared with samples not containing Al, with the band of dominant intensity at about 660 nm. Hypothetically, this is a consequence of incorporation of thulium ions into the crystalline phases cBN and AlN, which are equally likely to be formed during synthesis. The observed photoluminescence spectrum of the indicated samples is the superposition of the photoluminescence spectra of the Tm³⁺ ions located in the crystal fields of cBN and AlN of different symmetries. The presence in the photoluminescence excitation spectra (at 450, 490, and 660 nm) of structure, with features at wavelengths shorter than the excited photoluminescence, suggests a nonresonant mechanism for its excitation. We have established that luminescence of Tm³⁺ ions is less intense than for other rare earth elements incorporated into cubic boron nitride. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 4, pp. 547–555, July–August, 2008.     

Luminescence and lasing properties of neodymium- and uranium-activated inorganic laser liquids

An attempt was made to describe and show the possibilities of new inorganic neodynium- and uranium-activated laser liquids: SO₂-GaCl₃-NdCl₄; SO₂Cl₂-GaCl₃-NdCl₃-UO₂Cl₂; POCl₂-MCl_n-NdCl₃-UO₂Cl₂ for development and synthesis of direct nuclear reaction-excited lasers. Luminescence data presented in the work were used to calculate the luminescence parameters of the laser liquids such as oscillator strengths f, probability of spontaneous radiation A, intermultiplet luminescence branching coefficient β, cross-section for induced radiation σ, luminescence decay time τ, quantum yield η, and others. It is shown that the oscillator strengths of the normal absorption bands of Na³⁺, which play the main part in the pumping processes, exceed the oscillator strengths of Na³⁺ for aqueous and many other nonaqueous systems. In the luminescence excitation spectra of the Na³⁺ ion, bands are isolated in the range 400–1000 nm atλ _rec =1.06 μm. With excitation, luminescence occurs through the⁴F_3/2→⁴I_{9/2,11/2.13/2} channels. Luminescence spectral data are related to the lasing parameters. The threshold lasing energy is∼18 J/cm³. For a resonator with mirros h₁=100% and h₂=20, 40, 56, and 80%, the lasing energy is∼20–120 MJ/cm³ in the pumping energy range 18–180 J/cm³. The differential efficiency is ∼0.2% The substantial angular radiation divergence (θ∼4·10⁻² rad) and strong thermostatic distortions that occur in the active element (dn/dT≈−1.9·10⁻⁴K⁻¹) are a disadvantage of laser liquids. It is shown that operation of neodymium- and uranium-activated inorganic liquid lasers is stable under the present conditions. A. I. Gertsen Russian State Pedagogical University, Moika Embankment, 48, St. Petersburg, 191186, Russia. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 5, pp. 607–619, September–October, 1997.     

Luminescence of short-lived color centers induced in LiF crystals by a pulsed microwave discharge

A new phenomenon — intense luminescence of noncolored lithium fluoride (LiF) crystals excited by an electrodeless pulsed microwave discharge at the prebreakdown stage of development — is observed. This luminescence consists of the luminescence of short-lived aggregate F₂ and F ₃ ⁺ color centers at room temperature. It is shown that the density of short-lived color centers induced in the surface layer of LiF crystals by a microsecond microwave discharge reaches values of ∼10¹⁹−10²⁰ cm⁻³. Pis’ma Zh. éksp. Teor. Fiz. 66, No. 3, 163–167 (10 August 1997)     

Luminescence spectra and crystal structure of high-temperature superconductors

The luminescence spectra are obtained in the visible region for the high-T _c superconductors La₂CuO₄, YBA₂Cu₃O_7−δ , Bi₂Sr₂CaCu₂O_8±δ , and YBa₂Cu₃O_8±δ and for the secondary phases BaCuO_2±γ and Y₂Cu₂O₅. The presence of a luminescence band with energy E _lum∼2.4 eV in the spectra of all the investigated compounds is established. The nature of the observed luminescence bands is discussed on the basis of a comparative analysis of the crystal structures and luminescence spectra and on the basis of notions as to the presence of bands in the spectra accompanied by photoinduced diffusion of weakly bound oxygen and photoinduced charge transfer in the CuO₂ planes. Fiz. Tverd. Tela (St. Petersburg) 39, 1739–1746 (October 1997)     

The special features of the luminescence and light resistance of europium complexes and their mixtures with lanthanum complexes in polymethyl methacrylate

The kinetics of luminescence and transformation of short-lived products of the photolysis of europium and lanthanum complexes with thenoyltrifluoroacetone and 1,10-phenanthroline and their mixtures in polymethyl methacrylate films was studied by the nanosecond laser photolysis method with recording both light emission and absorption. Fast (535 and 585 nm, ⁵ D ₁ → ⁷ F ₀, ⁷ F ₃, decay time 0.7 μs) and slow (613 nm, ⁵ D ₀ → ⁷ F ₂, luminescence rise and decay times 0.7 μs and 0.5 ms, respectively) luminescence was studied. Induced absorption with a maximum at 600 nm and decay time ∼3 ms was observed; this absorption was assigned to triplet states of the deprotonated form of thenoyltrifluoroacetone. The dependences of luminescence intensity on the concentration of the components in a mixture of complexes were analyzed, and synergistic effects of luminescence strengthening were estimated. The kinetics of a decrease in luminescence intensity during photolysis was studied. Possible mechanisms of a decrease in the relative initial process rate and an increase in the quasi-stationary value of relative luminescence intensity as the concentration of complexes in the polymer increased were discussed.     

Sensitive Determination of Norfloxacin by the Fluorescence Probe of Terbium (III)- Sodium Dodecylbenzene Sulfonate and Its Luminescence Mechanism

The fluorescence system of the norfloxacin-Tb³⁺- sodium dodecylbenzene sulfonate (SDBS) was investigated in this paper. The experiments indicated that the fluorescence intensity of the Tb³⁺-SDBS was greatly enhanced by the norfloxacin. On the basis of the above findings, a sensitive fluorimetric method for determining the norfloxacin was established. The fluorescence intensity was measured by a 1-cm quartz cell with the excitation wavelength of 290 nm and the emission wavelength of 545 nm. The enhanced fluorescence intensity of the system (Δ F) showed a good linear relationship with the concentration of norfloxacin in the range of 5.0×10⁻⁹ mol L⁻¹–2.0×10⁻⁶ mol L⁻¹, its correlation coefficient was 0.9991 and the detection limit (S/N=3) was 1.2×10⁻⁹ mol L⁻¹. The presented method was used to determine the norfloxacin in real pharmaceutical samples. The luminescence mechanism was also discussed in detail. In the fluorescence system of the norfloxacin-Tb³⁺-SDBS, the SDBS not only acted as the surfactant, but also acted as the energy donor.     

Luminescence properties of calcium-iodide crystals

The effect of the conditions of preparation, temperature, and the action of x rays on the luminescence properties of calcium-iodide scintillation crystals is investigated. On the basis of the results of a study of the spectral characteristics of CaI₂ and CaI₂:H₂ crystals for optical and x-ray excitation in the temperature range 90–400 K, also taking into account the results of a study of the luminescence properties of CaI₂ crystals activated by Cl⁻, Br⁻, OH⁻, and Ca²⁺ impurities, it is suggested that the 236-nm band observed in the excitation spectra of crystals of calcium iodide may be caused by an uncontrollable hydrogen impurity. The luminescence of these crystals with maximum at 395 nm is ascribed to radiative recombination of excitons trapped at H⁻ ions. Zh. Tekh. Fiz. 69, 135–136 (January 1999)     

Luminescence of fluctuation tails of disordered solid solutions

The form of the stationary luminescence spectra of excitons, localized by composition fluctuations, in disordered solid solutions under weak excitation is calculated. The tail states for which there are no nonradiative transition channels are distinguished by means of continuum percolation theory. Such states are responsible for the “zero-phonon” luminescence band. The shape of the short-wavelength luminescence band edge is determined mainly by the number of isolated localizing clusters and their smallest complexes, which decreases rapidly near the mobility threshold. The real luminescence spectrum is due to the simultaneous emission of phonons. The phonon emission determines the form of the long-wavelength wing of the emission band. The computed shape of the emission spectrum is compared with the experimental luminescence spectra of the solid solution CdS_(1−c)Se_c. Pis’ma Zh. éksp. Teor. Fiz. 65, No. 3, 274–279 (10 February 1997)     

Luminescence of praseodymium (III) in solutions of mixed-ligand complexes with β-diketones

We have found that it is possible to enhance the luminescence of Pr(III) in solutions of complexes with β-diketones: acetylacetone derivatives containing fluoroalkyl substituents of different lengths and structures. We have established that in the presence of organic solvents, second (additional) ligands, and surfactants shielding the central ion from the quenching effect of the water molecules (OH oscillators), the intensity of luminescence for Pr(III) increases by a factor of 65, 38, and 45 respectively. In this case, cationic surfactants form ionic associates with Pr(III) β-diketonates, with incorporation of one more β-diketone molecule (ratio Pr:β-diketonate:surfactant = 1:4:1). As a result of suppression of intramolecular energy losses in solutions of Pr(III) β-diketonates, it is possible to observe its rather intense luminescence at 605 nm (the transition ¹D₂ → ³H₄), 612 nm (³P₀ → ³H₆), and 646 nm (³P₀ → 3F₂). __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 6, pp. 746–750, November–December, 2006.     

Synthesis and Chiral Recognition Properties of Novel Fluorescent Chemosensors for Amino Acid

The charge neutral chiral optical sensors 1a∼d containing thiourea and amide groups were synthesized by simple steps in good yields and their structures were characterized by IR, ¹H NMR, ¹³C NMR, MS spectra and elemental analysis. The enantioselective recognition for α-phenylglycine and phenylglycinol was examined by fluorescence emission and UV-vis spectra. The fluorescence and UV-vis spectra changes of 1a were obvious when the enantiomers of α-phenylglycine anion were added, which exhibited that 1a has good enantioselective recognition ability towards α-phenylglycine. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Influence of Oxygen Vacancies on the Luminescence Spectra of Y2O3 Thin Films

Luminescence spectra of Y₂O₃ thin films annealed in air and in vacuum are investigated. It is established that the presence of oxygen vacancies leads to a decrease in the intensity of the luminescence band with a maximum at 3.4 eV (related to emission of selflocalized Frenkel excitons describing the excited state of a molecular ion (YO₆)^9–) and of the luminescence band with a maximum at 2.9 eV (related to the anion sublattice). It is revealed that the oxygen vacancies also lead to a decrease in the luminescence intensity in the 2.60, 2.35, 2.10. 1.90, and 1.70 eV bands that are related to radiative recombination in the donor–acceptor Y³⁺–O^2– pairs. The donor–acceptor distances are calculated.     

Upconversion due to energy transfer involving Pr<Superscript>3+</Superscript> ions in pairs

Upconversion luminescence in triply ionized praseodymium-doped TeO₂–Li₂O glass using excitation at ∼590 nm into the ¹D₂ level from a dye laser pumped with the second harmonic of a pulsed Nd:YAG laser has been reported. The mechanism involved in the upconversion emission observed at ∼480 nm indicates that the most important contribution is energy transfer among praseodymium ions in pairs followed by the dipole–dipole interaction. The rate-equation model for the emission at ∼480 nm that provides direct information to determine the energy-transfer rates containing the pair of states involved in the upconversion process has been explored.     

Synthesis and Fluorescence Properties of Lanthanide (III) Perchlorate Complexes with Naphthyl-Naphthalinesulphonylpropyl Sulfoxide

A ligand with double sulfinyl groups, naphthyl-naphthalinesulphonylpropyl sulfoxide(dinaphthyl disulfoxide, L), was synthesized by a new method and its several lanthanide (III) complexes were synthesized and characterized by element analysis, molar conductivity, coordination titration analysis, IR, TG-DTA, ¹HNMR and UV spectra. The composition of these complexes, were RE₂(ClO₄)₆·(L)₅·nH₂O (RE = La, Nd, Eu, Tb, Yb, n = 2 ∼ 6, L = C₁₀H₇SOC₃H₆SOC₁₀H₇). The fluorescent spectra illustrated that the Eu (III) complex had an excellent luminescence. It was supposed that the ligand was benefited for transferring the energy from ligand to the excitation state energy level (⁵D₀) of Eu (III). The Tb (III) complex displayed weak luminescence, which attributed to low energy transferring efficiency between the average triplet state energy level of ligand and the excited state (⁵D₄) of Tb (III). So the Eu (III) complex displayed a good antenna effect for luminescence. The phosphorescence spectra and the relationship between fluorescence lifetime and fluorescence intensity were also discussed.     

Preparation and Time-Resolved Luminescence Bioassay Application of Multicolor Luminescent Lanthanide Nanoparticles

Because highly luminescent lanthanide compounds are limited to Eu³⁺ and Tb³⁺ compounds with red (Eu, ~615 nm) and green (Tb, ~545 nm) emission colors, the development and application of time-resolved luminescence bioassay technique using lanthanide-based multicolor luminescent biolabels have rarely been investigated. In this work, a series of lanthanide complexes covalently bound silica nanoparticles with an excitation maximum wavelength at 335 nm and red, orange, yellow and green emission colors has been prepared by co-binding different molar ratios of luminescent Eu³⁺–Tb³⁺ complexes with a ligand N,N,N¹,N¹-(4′-phenyl-2,2′:6′,2′′-terpyridine-6,6′′-diyl)bis(methylenenitrilo) tetrakis (acetic acid) inside the silica nanoparticles. The nanoparticles characterized by transmission electron microscopy and luminescence spectroscopy methods were used for streptavidin labeling, and time-resolved fluoroimmunoassay (TR-FIA) of human prostate-specific antigen (PSA) as well as time-resolved luminescence imaging detection of an environmental pathogen, Giardia lamblia. The results demonstrated the utility of the new multicolor luminescent lanthanide nanoparticles for time-resolved luminescence bioassays.     

Cathodoluminescence of ZnSe(Bi):Al crystals

The cathodoluminescence (CL) in ZnSe crystals annealed at T=1200 K in a Bi melt containing an aluminum impurity is investigated. The spectra are recorded for different excitation levels, temperatures, and detection delay times t ₀. As t ₀ is increased, the intensity of the orange band at λ _max=630 nm (1.968 eV) in the CL spectrum decreases in comparison to the intensity of the dominant yellow-green band at λ _max=550 nm (2.254 eV), whose half-width increases in the temperature range 6–120 K and then decreases as the temperature increases further. It is shown that such behavior of the yellow-green band is caused by the competition between two processes: recombination of donor-acceptor pairs and of free electrons with holes trapped on acceptors. The former mechanism is dominant at low temperatures, and the latter mechanism is dominant at high temperatures. At T∼120 mK the contributions of the two mechanisms to the luminescence are comparable. The resultant structureless band then achieves its greatest half-width, which is dictated by the interaction of the recombining charge carriers with longitudinal-optical and longitudinal-acoustic phonons and with the free-electron plasma. The mean number of longitudinal-optical phonons emitted per photon is determined mainly by their interaction with holes trapped on deep acceptors in the form of Al atoms replacing Se. The donor in the pair under consideration is an interstitial Al atom. Fiz. Tverd. Tela (St. Petersburg) 39, 1526–1531 (September 1997)     

Intrinsic luminescence of amorphous and disordered crystalline systems

A unified method is developed for describing the steady-state luminescence of exciton fluctuation states for weak excitation in different disordered systems. The phononless luminescence band is found to be formed by “radiative” states of the fluctuation tail in the density of states, i.e., by states for which nonradiative states are either nonexistent or have a low probability. The shape of the emission spectra calculated including the phonon interaction is in good agreement with experimental luminescence spectra of α Si:H and of solid solutions of ZnSe_(1−c)Te_c and CdS_(1−c)Se_c. Fiz. Tverd. Tela (St. Petersburg) 40, 890–891 (May 1998)     

Optical,nanostructural, and biophysical properties of Zn-induced changes in human erythrocyte membranes

We studied changes in the surface of erythrocyte membranes exposed to the action of zinc sulfate in the concentration range of 0.1–2.0 mM/l using methods of light scattering, spectrofluorimetry, and atomic force microscopy. Using the spectrofluorimetry method, we revealed a dose-dependent increase in the fluorescence intensity of a fluorescamine probe incorporated into erythrocyte membranes modified by zinc ions, which is indicative of an increase in the level of NH₂ groups on the cell surface. Using atomic force microscopy, we revealed changes in the surface topography of erythrocyte membranes exposed to the action of zinc sulfate in the concentration range of 0.1–2.0 mM/l. By performing a correlation analysis, we revealed that the correlation length of the autocorrelation function of the erythrocyte surface irregularity profile directly related to the fluorescence intensity of fluorescamine incorporated into erythrocyte membranes (r = 0.9, p < 0.05) modified by zinc ions. We showed that, in the zinc sulfate concentration range of 0.1–2.0 mM/l, zinc oxides form in erythrocyte membranes, which is confirmed by the appearance of an absorption band at 330–340 nm and by an increase in the light scattering. At more considerable concentrations, we identified absorption bands characteristic of zinc protein complexes in erythrocyte membranes. A considerable decrease in the elongation of the scattering indicatrix of erythrocyte membranes caused by luminescence correlates with the content of zinc proteins. Polarization measurements confirm the enhancement of the aggregation of protein complexes observed by the atomic force microscopy method. The proposed complex approach can be used in studies on the action of various abiotic factors on biological cells.     

Spectral-luminescence properties of a norbornene-substituted tetraazachlorin and its metal complexes

The spectral-luminescence properties of a tetraazachlorin derivative with a norbornene fragment annelated to a reduced pyrrole ring and its complexes with zinc and palladium have been studied at 293 and 77 K. For the norbornene-substituted free base, differences in fluorescence from unsubstituted tetraazachlroin and its dibenzobarrelene-substituted analog are found. The fluorescence lifetime is observed to rise by ∼7 times for the free base and by ∼1.6 ties for the Zn complex on going from 293 to 77 K. An essential dependence of the photophysical parameters on the nature of the solvent is noted. The fluorescence polarization spectrum of the norbornene-substituted tetraazachlorin reveals in the Soret band region at least four electronic transitions. For the Pd complex, weak phosphorescence in the near IR region has been detected; the 0–0 band maximum is at 990 nm and the singlet–triplet interval amounts to 5800 cm^–1, which is larger by 400 cm^–1 than for Pd tetraazaporphine. The quantum yields of the photosensitized formation of singlet oxygen have been determined using a relative luminescence method.     

Deformation Luminescence in gamma-irradiated KCl single crystals

Abstract

Deformation Luminescence(DL) is studied on KCl crystal colored by γ-irradiation. The spectra analysis of DL and thermoluminescence reveals that F-center plays a role as electron donor through the interaction with moving dislocation and V₂-center is a probable luminescence center. A theory is presented for understanding the deformation rate and temperature dependences of DL intensity.