Luminescence of biologically active 24-epicastasterone and a model compound

Biologically active brassinosteroid 24-epicastasterone, ring B of which contains a C=O group and has the nπ*-configuration for a low-lying electronic excited state, exhibits rapid fluorescence. The wavelengths of the fluorescence maxima of the steroid dissolved in hexane and acetonitrile are equal to 332 and 394 nm, respectively. The fluorescence lifetime of the steroid dissolved in acetonitrile is τ = 9.9 nsec. Solutions of 24-epibrassinolide do not luminesce. The long-wavelength electronic absorption band λ_max^abs = 340 nm in the absorption spectrum of an ethanol solution of model compound 2, ring D of which contains a C=O group π*-conjugated with the C=C double bond of ring C, like in the spectrum of the steroid, has a low extinction coefficient. An ethanol solution of 2 does not fluoresce. 24-Epicastasterone at 77 K in ethanol solution exhibits phosphorescence with λ_max^phos = 447 nm. The phosphorescence decay is exponential with τ = 0.79 msec. Compound 2 also phosphoresces. The phosphorescence spectrum of its ethanol solution has a maximum at 490 nm. The phosphorescence decay is nonexponential in the early stage. The phosphorescence lifetime is 25 msec in the exponential decay region. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 2, pp. 182–186, March–April, 2008.     

Fluorescence of N,N-di(2-carboxyethyl)-<Emphasis Type="Italic">p</Emphasis>-anisidine in solution and crystalline states

The fluorescence properties of N,N-di(2-carboxyethyl)-p-anisidine (I) in solvents of various nature and in the crystalline state have been studied at room temperature (273 K) and at the boiling point of liquid nitrogen (77 K). Fluorescence in aqueous solutions of I with protonated (λ _ex /λ _fl ^max = 225/290 nm) and unprotonated (λ _ex /λ _fl ^max = 270/380 nm) amino nitrogen has been detected. On going from aqueous solutions to nonaqueous, the fluorescence band of unprotonated I experiences a blue shift and its intensity rises. The fluorescence intensity of the band in aprotic polar solvents is higher than that in protic solvents. A linear dependence of the fluorescence intensity of deprotonated I on Cu(II) concentration (ranging from 1.0 to 5.0 mg/dm³) in aqueous solution has been found. The fluorescence intensity of I in aqueous solutions at 77 K and pH 1–6 has been shown to increase in the presence of Zn(II) (1–170 mg/dm³) and Cd(II) (2–330 mg/dm³) although a similar dependence is not observed at 293 K.     

Spectral-luminescent parameters of the amniotic fluid

Absorption and luminescence excitation and emission spectra of the amniotic fluid from females with a normal course of pregnancy and with fetation anomalies are investigated. It is shown that the amniotic fluid manifests, in addition to an intense UV luminescence, a luminescence in the range of 380–650 nm. The first luminescence peak with λ_max = 430–450 nm is most likely due to the presence of NADH₂ and hormones in the amniotic fluid, whereas the peak located at longer wavelengths with λ_max = 520–540 nm is due to pigments (bilirubin, etc.). Differences in absorption spectra of the amniotic fluid in the case of the normal course of pregnancy and upon its pathologies are established. Luminescence emission and excitation spectra of the amniotic fluid in cases of intrauterine fetation pathologies are shifted toward the longwave region compared to normal pregnancy cases. It is concluded that the spectral-luminescent analysis of the amniotic fluid can be used as an additional rapid test for monitoring of intrauterine fetal pathologies. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 6, pp. 939–942, November–December, 1998.     

Spectral and kinetic characteristics of CdI<Subscript>2</Subscript> and CdI<Subscript>2</Subscript>:Pb scintillators

We have studied the effect of lead dopant on the optical absorption, photoluminescence, and x-ray luminescence spectra, and the scintillation characteristics of CdI₂ at room temperature. The crystals for the study were grown by the Stockbarger-Bridgman method. Activation of CdI₂ from the melt by the compound PbI₂ leads to the appearance in the absorption spectra in the near-edge region of an activator band at 395–405 nm, which is interpreted as an A band connected with electronic transitions from the ¹S₀ state to the ³P₁ levels in the Pb²⁺ ion. For x-ray excitation, CdI₂:Pb²⁺ crystals with optimal dopant concentration (∼1.0 mol%) are characterized by a light yield with maximum in the 570–580 nm region that is an order of magnitude higher than for CdI₂ crystals in the 490–500 nm band. For α excitation, the radioluminescence kinetics for cadmium iodide is characterized by a very short (∼0.3 nsec) rise time and fast decay of luminescence, with τ₁ ≈ 4 nsec and τ₂ = 10–76 nsec. Depending on the conditions under which the crystals were obtained, the fast component fraction is 95%–99%. The crystal is characterized by a similar scintillation pulse in the case of excitation by x-ray pulses. The radioluminescence pulse shape for CdI₂:Pb in the decay stage is predominantly exponential, with luminescence decay time constants τ₁ ≈ 10 nsec and τ₂ = 200–250 nsec. This system is characterized by low afterglow, at the level for the Bi₄G₃O₁₂ scintillator. We have demonstrated the feasibility of using CdI₂:Pb as a scintillator for detecting α particles. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 6, pp. 825–830, November–December, 2008.     

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.     

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.     

Radiative properties of organic molecules in strong photon fields

We have experimentally investigated the dependence of the luminescence intensity of ethanol solutions of 2-(4-pyridyl)-5-phenyloxazole on the intensity of the exciting radiation from an XeCl laser (λ_ex = 308 nm, τ_p = 10 nsec, E_ex=10²²–10²⁶ photons/cm²·sec). We discuss the measurement technique and possible reasons for the change in radiative properties of the investigated solutions under the given conditions. V. D. Kuznetsov Siberian Physicotechnical Institute at Tomsk State University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 4, pp. 69–74, April, 1997.     

Time-Resolved Vacuum Ultraviolet Spectroscopy of Er<Superscript>3+</Superscript> Ions in the SrF<Subscript>2</Subscript> Crystal

The photoluminescence and photoexcitation spectra as well as the luminescence decay kinetics of Er³⁺ ions in the visible ultraviolet and vacuum ultraviolet (VUV) regions have been studied by the method of low-temperature, time-resolved VUV-spectroscopy on excitation by synchrotron radiation. In the VUV spectral region of the luminescence of SrF₂:1% Er³⁺, the 146.5-nm band with a time of decay of less than 0.6 nsec was revealed together with the well-known emission band at 164.3 nm (decay constant in the microsecond range). Its possible nature is discussed. The specific features of the formation of photoexcitation spectra of the f-f and f-d transitions in the Er³⁺ ion are considered. Competition between the processes of excitation of f-f and d-f luminescence has been revealed. It manifests itself in the inverse relationship of their photoexcitation spectra in a range of energies of incident photons that are close to the position of the 4fⁿ⁻¹5d configuration levels. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 4, pp. 519–523, July–August, 2005.     

Delayed Luminescence of 8-Aza-D-Homogone-1,3,5(10),13-Tetraene-12,17a-Dione in the Gas Phase and Solid Solutions

It is shown that the delayed-luminescence spectrum of 8-aza-D-homogone-1,3,5(10),13-tetraene-12,17a-dione (8-aza-D-homogonane) in the gas phase comprises a band of thermally activated delayed fluorescence and a band of annihilation delayed fluorescence that are respectively due to the C- and D-centers representing products of photo-and thermotransformations of the initial steroid for which we failed to detect delayed luminescence. The triplet-triplet energy transfer from the C-centers to the D-centers has been detected and its efficiency has been determined. It has been established that, in a frozen hexane solution (T = 77 K) of the substance taken from a vacuum cuvette after the investigation of initial 8-aza-D-homogonane in the gas phase, only the C- and D-centers phosphoresce. For a frozen solution of the initial steroid in a vitrifying mixture of tetrahydrofuran and toluene, a phosphorescence of both the steroid itself (λ _max ^phos = 415 nm) and the C- and D-centers (λ _max ^phos = 498 and 532 nm, respectively) was detected. This indicates that even the initial steroid kept at room temperature contains products of its transformation whose concentration increases on irradiation and heating. The C- and D-centers are stable molecules.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 2, pp. 192–197, March–April, 2005.     

Fluorescence spectroscopy of potential electroluminescent materials: Substituent effects on DSB and segmented PPV derivatives

The absorption and fluorescence of substituted distyrylbenzene (DSB) derivatives and segmented poly(phenylene vinylene) (PPV) derivatives are characterized by long-wavelength absorption maxima and absorption coefficients of λ_a = 380–450 nm, ε = 20,000–60,000 M⁻¹ cm¹ and fluorescence maxima, quantum yields, and decay times of λ_r = 440–530 nm, Φ_f = 0.2–0.9, and Τ = 0.8–2.5 ns, respectively. Alkoxy substituents at the central phenylene ring of DSB groups increase the bathochromic shift in the spectra in comparison to DSB, without a significant decrease in the high DSB fluorescence quantum yield. Both phenyl and cyano substitutions at the vinylene bridge lead to a further bathochromic shift of the fluorescence and a decrease in the quantum yield to ca. 0.4. The DSB derivatives and the related segmented PPV derivatives show nearly the same absorption spectra, fluorescence spectra, and radiative rate constantsk _f= Φ_f/Τ, indicating the efficacy of the segmentation of the polymer chain. The radiative rate constants determined by the Φ_f and Τ values and by the Strickler/Berg formula are in reasonable agreement. This supports the possibility of interpreting the properties of the polymers in terms of their DSB units. The decrease in the emission anisotropy can be ascribed to multistep energy transfer processes between different oriented segments.     

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.     

Synthesis,X-Ray Crystal Structures and Optical Properties of Novel Substituted Pyrazoly 1,3,4-Oxadiazole Derivatives

Novel pyrazoly 1,3,4-oxadiazole derivatives were synthesized and characterized by ¹H NMR, IR, HRMS and X-ray diffraction analysis. UV–vis absorption and fluorescence properties of these compounds in different solutions showed that the maximum absorption wavelength was not significantly changed in different solvents; however, maximal emission wavelength was red-shifted with the increase of solvent polarity. Absorption λ_max and emission λ_max was less correlated with substituent groups on aryl rings.     

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.     

Effect of alkali-metal doping on photoluminescence of CdS films

It is established that doping of CdS polycrystalline films with alkaline metals (Li, Na, K, Cs) results in an increase of luminescence intensity by 3–5 times compared with pure films. This increase is accounted for by the placement of alkaline-metal ions in V _Cd ²⁻ cation vacancies, which are nonradiative recombination centers in these films. From the dependences of the luminsecence intensity of the doped films on the synthesis conditions (deposition temperature, concentration of doping impurities, type of doping metal), the parameters that ensure the maximum luminescence intensity of the films are determined as T_dep ≈ 450°C and C_Me = 1·10⁻⁵ at %. The luminescence intensity decreases by 1–3% upon exposure of the films to UV light (λ_max = 365 nm, I = 10²¹ quanta·sec·cm⁻¹) for several hours. This is indicative of the stability of these films against UV radiation. __________ Translated from Zhurnal Prikladnoi Spektroskopii Vol. 74, No. 3, pp. 362–366, May–June, 2007.     

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.     

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.      

Determination of the optical bandgap for diamond-like carbon films obtained by laser plasma deposition

We have obtained and analyzed the optical transmission spectra of diamond-like carbon films deposited on quartz substrates by pulsed laser deposition (λ = 1064 nm, τ = 20 nsec, q = 4.9·10⁸ W/cm²) under vacuum (p = 2.6·10⁻³ Pa). Based on the spectra obtained, we have estimated the size of the bandgap by the Tauc method, and also have studied the growth dynamics of the coatings formed. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 5, pp. 637–641, September–October, 2007.     

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.     

Spectrofluorimetric methods of stability-indicating assay of certain drugs affecting the cardiovascular system

Two stability-indicating spectrofluorimetric methods have been developed for the determination of ezetimibe and olmesartan medoxomil, drugs affecting the cardiovascular system, and validated in the presence of their degradation products. The first method, for ezetimibe, is based on an oxidative coupling reaction of ezetimibe with 3-methylbenzothiazolin-2-one hydrazone hydrochloride in the presence of cerium (IV) ammonium sulfate in an acidic medium. The quenching effect of ezetimibe on the fluorescence of excess cerous ions is measured at the emission wavelength, λ_em, of 345 nm with the excitation wavelength, λ_ex, of 296 nm. Factors affecting the reaction were carefully studied and optimized. The second method, for olmesartan medoxomil, is based on measuring the native fluorescence intensity of olmesartan medoxomil in methanol at λ_em = 360 nm with λ_ex = 286 nm. Regression plots revealed good linear relationships in the assay limits of 10–120 and 8–112 g/ml for ezetimibe and olmesartan medoxomil, respectively. The validity of the methods was assessed according to the United States Pharmacopeya guidelines. Statistical analysis of the results exposed good Student’s t-test and F-ratio values. The introduced methods were successfully applied to the analysis of ezetimibe and olmesartan medoxomil in drug substances and drug products as well as in the presence of their degradation products.     

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.