Spectral and kinetic properties of fluorescence of immunoactive steroids in the gas phase

We have used steady-state fluorescence spectroscopy and pulsed kinetic fluorimetry with high time resolution to experimentally study the spectral and temporal characteristics of luminescence of immunoactive 8-aza-D-homogona-1,3,5(10), 13-tetraene-12,17a-dione (8-aza-D-homogonane) molecules in the gas phase. We have established the existence of several centers emitting long-wavelength and short-wavelength fluorescence. The fluorescence of high-temperature 8-aza-D-homogonane vapor (T = 550 K) when excited by radiation with λ_ex = 266 nm is represented by two spectrally separated emission bands with maxima λ _max ^fl = 465 nm and λ _max ^fl = 365 nm. Analysis of the distribution of fluorescence decay times for 8-aza-D-homogonane showed that in the spectral range of the emission wavelengths 360–590 nm, the fluorescence decay kinetics contains three components with average lifetimes <200 psec, 2.8 nsec and 13.5 nsec. The multicenter nature of luminescence of 8-aza-D-homogonane was confirmed by direct measurements of instantaneous fluorescence spectra in different stages of luminescence decay. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 3, pp. 309–314, May–June, 2006.     

Anti-stokes luminescence of solid AgCl<Subscript>0.95</Subscript>I<Subscript>0.05</Subscript> solutions

An anti-Stokes luminescence band with λ_max = 515 nm of microcrystals of solid AgCl_0.95I_0.05 solutions excited by a radiation flux of density 10¹³–10¹⁵ quanta/cm²·sec in the range 600–800 nm at 77 K was detected. It is shown that the intensity of this luminescence and the frequency of its excitation depend on the prior UV-irradiation of samples. Analysis of the stimulated-photoluminescence spectra and the anti-Stokes luminescence excitation spectra of the indicated microcrystals has shown that to the centers of anti-Stokes luminescence excitation correspond local levels in the forbidden band of the crystals. These states are apparently due to the atomic and molecular disperse silver particles that can be inherent in character or formed as a result of a low-temperature photochemical process. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 6, pp. 738–742, November–December, 2005.     

Luminescence of europium and ytterbium ions in strontium hexaborate

We have studied the luminescent properties of Eu^2+/3+ and Yb²⁺ ions in strontium hexaborate SrB₆O₁₀ for excitation in the 120–400 nm region. The luminescence spectra of Ln²⁺ ions in SrB₆O₁₀ consist of overlapping bands in the 370–520 nm region, due to 5d → 4f transitions at several nonequivalent centers. In the excitation spectra, besides the bands associated with 4f → 5d transitions in the Ln²⁺ ions, we also observe a band in the 135–160 nm region due to the transitions O(2p) → B(2s,2p) within the borate anions. The luminescence of the Eu³⁺ ions is excited most efficiently in the region of the Eu³⁺ charge transfer band (λ_max = 226 nm). The results obtained are compared with data for Ln in other strontium borates. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 6, pp. 770–774, November–December, 2006.     

Synchrotron and laser excitation of luminescence in PbWO<Subscript>4</Subscript>:Tb crystals at different temperatures

The effect of temperature on the spectral luminescence characteristics of PbWO₄:Tb³⁺ crystals with synchrotron and laser excitation is studied. If PbWO₄:Tb³⁺ is excited by synchrotron radiation with λ = 88 nm at 300 K, a faint recombination luminescence of the impurity terbium is observed against the matrix luminescence. When the temperature is reduced to 8 K, the luminescence intensity of PbWO₄:Tb³⁺ increases by roughly an order of magnitude and the characteristic luminescence of the unactivated crystal is observed. Excitation of PbWO₄:Tb³⁺ by a nitrogen laser at 300 K leads to the appearance of emission from Tb³⁺ ions. At 90 K, a faint matrix luminescence is observed in addition to the activator emission. The formation of the luminescence excitation spectra for wavelengths of 60–320 nm is analyzed and the nature of the emission bands is discussed.     

Intense blue-emitting Ca5Al8O14: Eu phosphor for mercury free lamp

The calcium aluminates doped with Eu ions, Ca₅Al₈O₁₄: Eu, phosphors are prepared by the combustion method. The formation of crystalline aluminates was confirmed by X-ray diffraction pattern. The prepared phosphors were characterized by SEM, TGA, DTA, particle size analyzer and Photoluminescence (PL) techniques. From the UV-excited luminescence spectra it was found that the Eu ions acts as a luminescent centre with luminescence at the blue (λ _max = 470 nm) region due to 4f ⁶5d ¹ → 4f ⁷ transition. The excitation spectra show the broad band at 355 nm wavelength (λ _em = 470 nm). The excitation 355 nm is a mercury free excitation and therefore Ca₅Al₈O₁₄: Eu may be useful for the solid state lighting phosphor in lamp industry.      

Luminescence of hafnium dioxide films produced from hafnium dipivaloylmethanate

A technique is developed for measuring luminescence spectra of hafnium dioxide using a hydrogen lamp as an excitation source. The luminescence spectra of the as-grown and annealed hafnium dioxide films prepared by chemical deposition from volatile hafnium dipivaloylmethanate on the Si(111) substrates are measured at room temperature. Intense luminescence at λ ≌ 280 nm is characteristic of nanocrystallites of monoclinic modification. The band gap width is found to be ≌ 5.76 eV. It is shown that the film composition significantly deviates from the stoichiometric one. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 4, pp. 63–67, April, 2007.     

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)     

Spectroscopic investigation of the plasma of a high-current diffuse discharge in He/Ar/CF2Cl2(CCl4) mixtures

Survey emission spectra in the region of 190–600 nm and time and service-life characteristics of a transverse nanosecond discharge in He/Ar/CF₂Cl₂(CCl₄) mixtures at a pressure of 10–100 kPa are investigated. In the emission spectra, excited products of the decomposition of freons—C₂(A−X), CN(B−X), Cl ₂ ^* , C^*, Cl^*, and Cl^+*— and the emission of ArF at λ=193 nm are revealed. The emissions of Cl ₂ ^* at λ=258 nm and ArF at λ=193 nm were the most intense. The discharge in the He/Ar/CF₂Cl₂ mixture is a multiwave emission source with λ=258 nm Cl ₂ ^* 193 nm ArF, and probably, 175 nm Arcl. It is of interest for applications in UV-VUV-range pulse photometry. The duration of the emission on Cl ₂ ^* , ArF, ArI, ClI, and ClII transitions in the discharge in the Ar/CF₂Cl₂ mixture (P=10–20 kPa) was 200–300 nsec. With adding He and increasing pressure to 100 kPa the duration of the emission decreased by a factor of 1.5–2. The basic mechanisms of the formation of Cl₂, ArF, and CN(B) molecules in the transverse-discharge plasma are considered. Uzhgorod State University, 46, Pidgirna Str., Uzhgorod, 294000, Ukraine. Translated from Zhurnal. Prikladnoi Spektroskopii, Vol. 66, No. 2, pp. 241–246, March–April, 1999.     

Spontaneous parametric light scattering in spatially inhomogeneous nonlinear media based on photonic crystals

The emission spectra of nonlinear media with periodical modulation of the second-order susceptibility that are based on synthetic opals infiltrated by Ba(NO₃)₂, LiIO₃, and KH₂PO₄ are studied using radiation with λ = 400 and 407 nm for excitation. The spectral angular distribution of the emission in the range of 420–650 nm is revealed, as well as the dependence of its spectrum on the photonic stop-band parameters and the exciting radiation characteristics. The emission spectrum of samples with a low dielectric contrast has the shape of a symmetric band with a maximum at 525 nm and a half-width of about 100 nm. The observed emission is interpreted as spontaneous parametric light scattering in a spatially inhomogeneous nonlinear medium.     

Luminescence of CsBr:Eu films grown by liquid-phase epitaxy

By liquid-phase epitaxy from an aqueous alcoholic solution, we have obtained films of the well-known storage phospor CsBr:Eu, and we have studied their cathodoluminescence and photoluminescence (PL) spectra compared with the undoped CsBr films. We have established that the structure of the photoluminescence centers of the CsBr:Eu films when excited by laser radiation in the absorption band of the Eu²⁺ ions (λ = 337 nm) includes Eu²⁺-V_Cs isolated dipole centers and CsEuBr₃ aggregate centers, and also luminescence centers based on inclusions of hydroxyl group OH⁻ with the corresponding emission bands in the 440 nm, 520 nm, and 600 nm regions. We have studied the dependence of the spectra and the intensity of the photoluminescence for CsBr:Eu films on annealing temperature in air at 423–483 K, compared with analogous dependences for CsBr:Eu single crystals obtained from the melt. We have shown that annealing the films at T = 423–463 K leads to rapid formation of CsEuBr3 aggregate luminescence centers, while for T > 473 K thermal degradation of these centers occurs. We conclude that the observed differences between the photoluminescence spectra of CsBr:Eu films and CsBr:Eu single crystals may be due to additional doping of the films with OH⁻ ions. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 2, pp. 191–194, March–April, 2006.     

Emission analysis of RE3+ (Eu3+, Tb3+ & Ho3+): B2O3-BaO-LiF/AIF3 glasses

We report here the luminescence spectra of certain rare earth ions (Eu³⁺, Tb³⁺ & Ho³⁺) doped B₂O₃-BaO-LiF/AiF₃ based on the measurements of emission and decay curves of prominent emission transitions. For both the reference host glasses, FTIR, XRD, DTA-TG profiles have been recorded to understand their structural and thermal properties. Eu³⁺ doped glasses have shown five emission transitions of ⁵D₀ → ⁷F_{01,2,3 & 4} located at 580nm, 593nm, 615nm, 655nm and 704nm respectively with an excitation at λ_exci = 392 nm (⁷F₀ → ⁵L₆). Also under an UV source, these europium glasses have displayed a bright red emission from their surfaces. Tb³⁺ glasses have exhibited four emission bands of ⁵D₄ → ⁷F_6,5,4,3 at 491nm, 547nm, 588nm and 625nm respectively with an excitation at λ_exci = 376 nm (⁷F₆ → ⁵G₆). Intense green emission from the glass surfaces has been noticed upon exposure to the UV source. Prominently bluish-green emission has been noticed from the surfaces of the holmium glasses under an UV source and same emission transition (⁵F₄ → ⁵I₈) at 519 nm with an excitation at λ_exci = 389 nm (⁵I₈ − ⁵G₄) has also been obtained from their measured emission spectra. For all the prominent emissions of the rare earth glasses, decay curves have been measured to compute their lifetimes.     

Luminescence properties of transparent ceramics Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Yb

We present the results of studying the luminescence properties of transparent ceramics Y₃Al₅O₁₂:Yb obtained by the vacuum sintering and nanocrystalline technology. In the course of research, we measured the luminescence and luminescence excitation spectra, as well as the temperature and kinetic behavior of luminescence. Our results are analyzed in comparison with the characteristics of corresponding single crystals. We revealed that processes of generation and relaxation of electronic excitations that occur in ceramics, in particular, in the charge transfer state, are similar to processes occurring in crystals. The behavior of two charge-transfer luminescence bands at 340 and 490 nm is studied. In the range 300–600 nm, we revealed a broad emission band of radiation of other type, which is also observed in spectra of undoped ceramics. This broad band is attributed to F⁺ centers. Emission and excitation spectra of charge transfer luminescence at a maximum of the temperature dependence of 100 K are measured for the first time. We found that, upon excitation in the charge transfer band, luminescence in ceramics is more intense than in single crystals with similar concentrations of Yb and has a higher quenching temperature.     

Luminescence and selective heat radiation of Yb<Subscript>2</Subscript>O<Subscript>3</Subscript> upon the resonant and thermal laser excitation

Yb₂O₃ polycrystals with a size of up to 10 mm are synthesized using the sintering and melting of the ultrapure Yb₂O₃ powders by the CO₂-laser radiation with the power P _L ≤ 100 W at the wavelength λ = 10.6 μm at the melting point T _m = 2703 K, forming due to surface tension in melt, and crystallization in air. The analysis of the polycrystal microstructure using the methods of optical and electron microscopy and X- ray diffractometry shows that perfect oxide crystallites are formed in the course of crystallization after melting-through. The transformation of the luminescence and selective heat radiation (SHR) spectra of the Yb₂O₃ polycrystals is studied under the resonant excitation at λ ≈ 975 nm using a laser diode and the laser heating at the wavelength λ = 10.6 μm. When the resonant excitation power of the Yb³⁺ ions increases from 0.15 to 4.5 W, the Stokes luminescence of the Yb₂O₃ polycrystals is sequentially transformed into SHR and the thermal radiation of the crystal lattice. The transformation of the emission spectra of the Yb₂O₃ polycrystals with an increase in the laser heating intensity by about four orders of magnitude can be represented as the low-temperature heat radiation, spectral burst of the thermodynamically nonequilibrium SHR of the Yb³⁺ ions, and the high-temperature radiation of the crystal lattice. The temperature dependence of the luminescence spectra and SHR of the Yb₂O₃ polycrystals on the intensity of the laser and laser-thermal excitation and the concentration quenching of the Yb³⁺ luminescence in oxides indicate the key role of the interaction of the f-electron shell of the Yb³⁺ ions with the natural oscillations of the crystal lattice in the processes of the multiphonon excitation and nonradiative (multiphonon) and radiative (vibronic) relaxation.     

Anti-stokes fluorescence of polymethine dyes excited by a titanium-sapphire laser

Fluorescence of symmetric polymethine dye solutions (λ _abs ^max ≈ 700 nm) upon anti-Stokes excitation by cw radiation of a titanium-sapphire laser (781 nm) is first investigated. A series of six compounds with analogous composition and spectral and luminescent properties is investigated. It is demonstrated that in addition to the anti-Stokes component, the Stokes component with a maximum at 820 nm (referred to the H-aggregates of initial dyes) is observed in the fluorescence spectra of solutions of the examined molecules when dye concentration increases to 10⁻³ M. Dependences of the anti-Stokes and Stokes component intensities on the exciting radiation power are obtained that confirm a linear excitation character. On examples of xanthene and polymethine dyes, the use of organic fluorophors for anti-Stokes laser cooling and some other possible applications of the anti-Stokes fluorescence are discussed. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 3, pp. 63–70, March, 2007.     

Luminescence properties of oxide coatings on aluminum alloys

This is a study of the luminescence properties of coatings formed on aluminum alloys by anodizing in electrolytic solutions based on oxalic, sulfuric, and tartaric-sulfonic acids. At least two emission centers, with band maxima in the ranges of 390–410 and 470–510 nm, can be reliably identified in the photoluminescence spectra. The first type of center is characterized by single-band photoluminescence excitation spectra and the second, by two-band spectra. An analysis of the two-band photoluminescence excitation (PLE) spectra in the range of 470–510 nm shows that the position of the narrow short-wavelength PLE spectrum near 272 nm is independent of the type of acid used in the anodization process. The position and shape of the other PLE spectral bands depend both on the type of acid used and on the processing of the alloy or alumina surfaces. It is assumed that defect-free alumina centers are responsible for the 272 nm PLE band, while the other photoluminescence bands are caused primarily by different divacancies of oxygen (F₂⁺ {F_2^+} , F ₂, and F₂⁺² {F_2^{+2}} centers) whose origin is governed by the type of electrolyte.     

Luminescence of mercuric iodide crystals

Low-temperature (4.2–130 K) photoluminescence spectra of HgI₂ crystals have been measured in the 540–700 nm region. An analysis of the characteristics (intensity vs temperature and excitation power relations, afterglow times, excitation spectra) of the 560, 620, and 635 nm emission bands suggests the following assignments: the 560 nm band is due to radiative annihilation of excitons bound to mercury vacancies, and the “red” emission originates from recombination of free (620 nm) and donor-localized (635 nm) electrons with a hole-filled acceptor level. The energies of the corresponding donor and acceptor levels have been estimated. New emission bands at 540, 545, and 575 nm have been discovered, and their origin discussed. Fiz. Tverd. Tela (St. Petersburg) 39, 67–73 (January 1997)     

Photoluminescence of a BaSiO3:Yb3+ crystal

We present the results of a study of the luminescence and luminescence excitation spectra, and also the luminescence kinetics of a BaSiO₃:Yb³⁺ crystal. We have established the mechanism for emission by the matrix and energy transfer from the matrix to the rare earth ion. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 4, pp. 478–482, July–August, 2006.     

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)     

Strong green luminescence of Ni2+-doped ZnS nanocrystals

ZnS nanoparticles doped with Ni²⁺ have been obtained by chemical co-precipitation from homogeneous solutions of zinc and nickel salt compounds, with S^2- as precipitating anion, formed by decomposition of thioacetamide (TAA). The average size of particles doped with different mole ratios, estimated from the Debye–Scherrer formula, is about 2–2.5 nm. The nanoparticles could be doped with nickel during synthesis without altering the X-ray diffraction pattern. A Hitachi M-850 fluorescence spectrophotometer reveals the emission spectra of samples. The absorption spectra show that the excitation spectra of Ni-doped ZnS nanocrystallites are almost the same as those of pure ZnS nanocrystallites (λ_ex=308–310 nm). Because a Ni²⁺ luminescent center is formed in ZnS nanocrystallites, the photoluminescence intensity increases with the amount of ZnS nanoparticles doped with Ni²⁺. Stronger and stable green-light emission (520 nm) (its intensity is about two times that of pure ZnS nanoparticles) has been observed from ZnS nanoparticles doped with Ni²⁺. Received: 18 December 2000 / Accepted: 17 March 2001 / Published online: 20 June 2001     

Luminescent crystals of MIIGa2S4:Er3+ (MII = Eu, Yb, Ca)

We have studied the photoluminescent properties of M^IIGa₂S₄:Er³⁺ polycrystals (M^II = Eu, Yb, Ca) for excitation by radiation with λ = 976 nm as a function of temperature. The samples were obtained by solid-state reaction. We have studied the comparative characteristics of the anti-Stokes and IR luminescence of these luminophores. We have determined the mechanisms for anti-Stokes emission of M^IIGa₂S₄:Er³⁺ crystals. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 3, pp. 332–335, May–June, 2007.