Influence of the mineral component in biotissues affected by calcinosis on their laser-induced fluorescence spectrum

Laser-induced fluorescence (LIF) spectra of human cardiac-valve tissues affected by calcinosis and of macroscopic calcinosis formations produced from resected cardiac valves with such pathology were investigated by comparison with analogous spectra of bone and myocardial tissue of an animal, LIF was excited by an excimer laser with λ=248 nm. In the spectrum of macroscopic calcinosis formations, luminescence bands of the mineral component were separted from the band of protein tissues when these tissues were subjected to heat treatment at 700°C. The investigations have shown that the LIF spectrum of a calcified tissue contains fluorescence bands of tryptophan and fluorescence bands of the mineral component (hydroxylapatite). A change in the spectrum of tissues with pathological processes can be cause not only by a relative change in the concentration of collagen elastin, but also by the additional fluorescenced of the hydroxylapatite mineral that is absent in a healthy cardiac tissue. It was found that the change in the spectrum characterized by the ratio of the LIF intensity at λ=330 nm to the LIF intensity at λ=450 nm is sufficiently large. This makes it possible to use measurements of the relative intensity of fluorescence at these wavelengths to control the degree of calcination of cardiac tissue. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 6, pp. 846–849, November–December, 1999.     

Fluorescence properties of biochemicals in dry NaCl composite aerosol particles and in solutions

Several fluorophores, such as tryptophan, NADH, NADPH, and riboflavin are found in airborne micro-organisms. In this work, the fluorescence properties of these biochemicals were studied both in dry NaCl composite aerosol particles and in saline solutions by means of laser-induced fluorescence. Fluorescence spectra were measured from individual, airborne aerosol particles and from solutions in cuvette. The excitation wavelength was varied in steps from 210 nm to 419 nm and the fluorescence was detected within a wavelength band of 310–670 nm. For each sample, the measured fluorescence emission spectra were combined into fluorescence maps. The fluorescence maximum of riboflavin in a dry NaCl composite particle is 20 nm red-shifted compared with the solution, whereas the maxima are blue-shifted by about 25 nm for tryptophan and 15 nm for NADH and NADPH. The molecular fluorescence cross sections have significant differences between the aerosol particles and the solutions, except for tryptophan. For NADH and NADPH the cross sections are over 20 times larger in the aerosol particles than in the solutions probably as a result of partial quenching of fluorescence in solution caused by the collision or stacking with the adenine moiety. The fluorescence cross section of riboflavin is almost 60 times larger in the solution than in the dry NaCl composite aerosol. This is probably caused by the different microenvironment around the fluorophore molecule and by the concentration quenching in the particles where the fluorescing molecules are relatively close to each other.     

Two-photon-excited luminescence spectra in diamond nanocrystals

Two-photon-excited luminescence (TEL) spectra have been recorded in the blue (400–500 nm) and near-ultraviolet (300–400 nm) ranges for diamond particles with 4 nm average size, which were obtained by detonation synthesis from explosives. The observed TEL bands are attributed, by comparing the obtained spectra with the impurity luminescence spectra in large diamond crystals, to N2 and N3 defects associated with the presence of nitrogen impurities in diamond. The TEL spectra presented are found to have certain distinguishing features: short-wavelength shift of the maximum and changes in the shape and width of the spectral bands for ultradispersed diamond compared with the spectrum in bulk crystals. Fiz. Tverd. Tela (St. Petersburg) 41, 1110–1112 (June 1999)     

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.     

Change in laser-induced fluorescence spectra of sea water during degradation of dissolved organic matter

We present the results of measurement of the laser-induced fluorescence spectra of sea water under laboratory conditions. We show that during phytoplankton cell death caused by heating of sea water samples, the fluorescence intensity of dissolved organic matter (DOM) increases. We observe different behaviors of the fluorescence intensity for excitation by 2nd harmonic (532 nm) and 3rd harmonic (355 nm) emission from a Nd:YAG laser during degradation of dissolved organic matter. In the first case, a monotonic decrease in the DOM₅₃₂ fluorescence intensity occurs, while in the second case the fluorescence intensity remains constant. We give a possible explanation for such behavior of the DOM fluorescence intensity. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 103–107, January–February, 2007.     

Fluorescent probe based on proton transfer in 4′-(diethylamino)-3-hydroxyflavone: Spectral and luminescent characteristics upon selective excitation

The spectral characteristics of acetonitrile solutions of 4′-(diethylamino)-3-hydroxyflavone dye with dual fluorescence are studied under selective excitation. This dye is a structural analog of 3-hydroxyflavone and exhibits excited-state proton transfer, which, in contrast to 3-hydroxyflavone, has a thermodynamic rather than a kinetic character. The fluorescence spectra at different excitation photon energies and the excitation spectra of different fluorescence bands are studied. It is found that the intensity ratio of the normal and tautomeric fluorescence bands lying near 507 and 570 nm, respectively, depends on the excitation wavelength, namely, this ratio is 1.45 and almost does not change in the region of the main absorption band (370–420 nm), while, in the region of the second singlet band (near 280 nm), it decreases to 1.15. This can be explained by an increase in the probability of proton transfer with formation of a tautomeric form in the case of excitation into the second band. Another interesting feature is the existence of a latent third emission band peaked at 535 nm, which was found and reliably recorded upon excitation at wavelengths of 470–500 nm. Addition of water quenches this emission, which indicates that it belongs to the anionic form of the dye.     

Solution electronic spectra of brassinosteroid and a synthesized conjugate of a steroid and a fluorescent label

Electronic absorption spectra of 24-epicastasterone and 24-epibrassinolide solutions have been recorded and analyzed. The long-wavelength band in solution spectra of the former steroid with maxima in the region 292–286 nm is assigned to the electronic nπ*-transition of a carbonyl chromophore. The latter steroid contains an O-C=O group, for which the extinction coefficient in this spectral region is approximately one order of magnitude less. These differences can be used to identify the studied steroids. A method to synthesize the conjugate of 24-epicastasterone with a fluorescent label, dansylhydrazine, which shows intense fluorescence and absorption, is described. Absorption spectra of the label and conjugate in diethylether, tetrahydrofuran, ethanol, and acetonitrile solutions are practically independent of the solvent properties. The exceptions are solutions of the conjugate in hexane and water. All investigated solutions of label and conjugate show intense fluorescence. As the dielectric constant of the solvent increases, the fluorescence spectra shift to long-wavelength. The fluorescence energetic and time characteristics of both the label and conjugate are similar, which enables the conjugate to be used in developing a method for immunofluorescent analysis of the brassinosteroid 24-epicastasterone. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 1, pp. 74–78, January–February, 2008.     

Fluorescence and absorption of polystyrene exposed to UV laser radiation

We show that when polystyrene is exposed (for 15–60 sec) to a UV laser light beam (λ = 248 nm), its absorption and luminescent properties change significantly. In the irradiated polymer, optical centers are formed with absorption bands in the 280–460 nm region and fluorescence bands in the 330–520 nm region. We have established the chemical structure of the optical centers for fluorescence of polystyrene. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 1, pp. 54–58, January–February, 2006.     

Spectral properties of molecular charge-transfer probe QMOM

The spectral characteristics of solutions of a dye with dual fluorescence, 1-methyl-2-(4-methoxy)phenyl-3-hydroxy-4(1H)-quinolone, in acetonitrile are studied upon selective excitation. This dye is a structural analogue of 3-hydroxyflavone and also exhibits excited-state proton transfer, which, as well as in the case of 3-hydroxyflavone, has a kinetic nature. The fluorescence spectra are studied upon excitation by photons of various energies, and the excitation spectra are recorded at wavelengths of different fluorescence bands. It is found that the intensity ratio of the emission of the normal and tautomeric forms (at wavelength of 415 and 518 nm, respectively) is almost the same (0.23–0.25) for excitation in the regions of the main and the second absorption bands. At the same time, in the case of excitation between these bands, this ratio decreases to 0.19. The second interesting feature is the existence of a third latent emission band peaked at about 480 nm, which is reliably detected upon excitation at wavelengths in the region of 400–450 nm. This study shows that this emission belongs to the anionic form of the dye. This form is also responsible for a decrease in the intensity ratio of the emission of the two main forms in the case of excitation between the first and second absorption bands.     

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.     

Luminescence in the 1.54 µm region for erbium in two-dimensional and three-dimensional mesoscopic structures

We have studied the luminescence and luminescence excitation spectra of erbium in the 1.54 μm region in titanium oxide and silicon oxide xerogels, formed in the mesoscopic pores of three-dimensional synthetic opals and two-dimensional porous aluminum oxide structures. For erbium-doped titanium oxide films formed in opal, in contrast to analogous films on porous aluminum oxide, in the luminescence excitation spectra we observe an intense broad band with a maximum in the ∼360 nm region. We discuss the possible nature of this band. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 5, pp. 622–626, September–October, 2007.     

Optical characteristics of a transverse discharge in neon at atmospheric pressure

We present the results of investigation into radiation of a pulsed transverse discharge in neon at a pressure of 10–200 kPa. Survey spectra of plasma radiation, time characteristics of radiation, and the effect of small impurities of water vapors and air on the optical characteristics of a neon plasma were studied. We show that at a pressure of residual gases at a level of 10 Pa intense OH*, NO*, and N _* ² bands are observed in radiation of the plasma of a nanosecond transverse discharge in Ne against the background of continuous plasma radiation, and in the spectral region with λ>400 nm radiation was observed on the H_β 486.1 nm and NeI 585.3 nm lines, and (when P≥100 kPa) on the line at the 3s–3p-transitions of a Ne atom. The radiation intensity of the third continuum of neon increases with pressure and with energy contribution to plasma, with its maximum being located in the VUV spectral region (λ _max <200 nm). To whom correspondence should be adressed. Uzhgorod State University, 46, Pidgirna St., Uzhgorod, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 1, pp. 5–10, January–February, 1999.     

Laser-induced fluorescence monitoring of the gas phase in a glow discharge during reactive sputtering of vanadium

Processes in the gas phase of a glow discharge during diode and magnetron reactive sputtering of vanadium in an Ar–O₂ atmosphere have been investigated by laser-induced fluorescence (LIF) as a function of the parameters of the glow discharge and the composition of the atmosphere. The intensity of the fluorescence spectra increased by 1.5–2.0 orders of magnitude in the magnetron sputtering process compared with that of diode sputtering. Under continuous sputtering conditions, the dependences of the intensities and relative compositions of the fluorescence spectra on the discharge parameters (discharge voltage and current) have been investigated. In pulsed mode of the glow discharge, the dynamics of changes in the spectra have been studied versus variations in the discharge duration and the lag time for recording the fluorescence signal. The dependence of the spectral line intensities on the partial pressure of oxygen has been found for vanadium and its oxide. The cathode surface at pressures of 0.03–0.04 Pa was shown to convert to the oxidized state.     

Fluorescence spectra of blood plasma treated with ultraviolet irradiation <Emphasis Type="Italic">in vivo</Emphasis>

We have studied the fluorescence spectra of blood plasma from patients with acute coronary syndrome, and also the effect of therapeutic doses of in vivo ultraviolet blood irradiation (UBI) on the spectra. We have established that the maxima in the fluorescence spectra of the original plasma samples, obtained from unirradiated blood, are located in the wavelength interval 330–340 nm, characteristic for the fluorescence of tryptophan residues. In extracorporeal UBI (λ = 254 nm), we observed changes in the shape and also both a blue and a red shift in the maxima of the fluorescence spectra, differing in magnitude for blood plasma samples from different patients in the test group. We show that UBI-initiated changes in the fluorescence spectra of the plasma depend on the original pathological disturbances of metabolite levels, and also on the change in the oxygen-transport function of the blood and the acid–base balance, affecting the oxidative stability of the plasma. We have concluded that UV irradiation, activating buffer systems in the blood, has an effect on the universal and specific interactions of the tryptophan residue with the amino acid residues and water surrounding it.     

Luminescence of Nile red as indicator of composition of nanoparticles from diketonate complexes of trivalent metals

We study the sensitization of fluorescence of Nile red in nanoparticles formed in aqueous solutions of complexes of Al, In, Sc, and Lu with DBM, DBM, and phen and of complexes of In with MBTA and phen. We show that, at concentrations of Nile red of 2–50 nM and complexes of 10–30 μM, the fluorescence intensity of Nile red in aqueous solutions increases by 1.5–2 orders of magnitude compared to its fluorescence in H₂O. We find that, at these concentrations of Nile red in solutions of complexes Al, the dye is completely contained in nanoparticles from these complexes. We show that Nile red molecules are inhomogeneously distributed in nanoparticles from complexes and, upon the completion of the formation of nanoparticles, dye molecules tend to be localized in regions of nanoparticles formed from diketonate complexes M(diketone)₃phen (M is Lu or In) and Al(DBM)₃. Upon the localization of Nile red in these regions, the maximum of its fluorescence spectrum shifts toward ∼600 nm and, upon the penetration of Nile red into nanoparticles from Sc complexes, the shift of the maximum of its fluorescence spectrum compared to the spectrum in water does not exceed 10 nm. The shifts of the spectra are collated with the ability of ions to form diketonate and hydroxy diketonate complexes. We demonstrate that the fluorescence of Nile red is efficiently sensitized, not only upon its penetration into nanoparticles formed from complexes, but also upon its adsorption on the nanoparticle surface when Nile red molecules are introduced in solutions of already formed nanoparticles.     

Laser-induced fluorescence measurements of velocity within a Hall discharge

The results of a study of laser-induced fluorescence velocimetry of neutral and singly ionized xenon in the plume and interior portions of the acceleration channel of a Hall thruster plasma discharge operating at powers ranging from 250 to 725 W are described. Axial ion and neutral velocity profiles for four discharge voltage conditions (100 V, 160 V, 200 V, 250 V) are measured as are radial ion velocity profiles in the near-field plume. Ion velocity measurements of axial velocity both inside and outside the thruster as well as radial velocity measurements outside the thruster are performed using laser-induced fluorescence with nonresonant signal detection on the xenon ion 5d[4]_7/2–6p[3]_5/2 excitation transition while monitoring the signal from the 6s[2]_3/2–6p[3]_5/2transition. Neutral axial velocity measurements are similarly performed in the interior of the Hall thruster using the 6s[3/2]⁰ ₂–6p[3/2]₂transition with resonance fluorescence collection. Optical access to the interior of the Hall thruster is provided by a 1-mm-wide axial slot in the insulator outer wall. While the majority of the ion velocity measurements used partially saturated fluorescence to improve the signal-to-noise ratio, one radial trace of the ion transition was taken in the linear fluorescence region and yields a xenon ion translational temperature between 400 and 800 K at a location 13 mm into the plume. Received: 27 September 2000 / Revised version: 2 March 2001 / Published online: 9 May 2001     

High-resolution spectroscopy on ground-state transitions of samarium-I

A high resolution laser-induced fluorescence study has been performed on thirteen ground-state transitions in samarium, using a frequency-doubled Ti:sapphire laser in the wavelength range 350–440 nm. From each spectrum isotope shifts and hyperfine structure constants A and B are derived. The results are used to determine the nuclear parameter λ^AA'.     

Complexation in two-component chlortetracycline-melanin solutions

The spectra and kinetics of fluorescence of two-component solutions of the chlortetracycline (CHTC)-DOPA-melanin (melanin or ME) system in water have been investigated. The data obtained have been compared to similar data for solutions of CHTC-melanosome from bull eye (MB), which contains natural melanin, in K-phosphate buffer at pH 7.4. The overall results indicate the occurrence of complexation between molecules of CHTC and ME as they are being excited. The studies of complexation in the solution of CHTC-MB in the buffer are complicated by the formation of a CHTC-buffer complex. The effect of optical radiation in the range 330–750 nm on the CHTC-ME complex shows selectivity: the greatest change in the spectrum occurs when the wavelength of the exciting radiation coincides with the long-wavelength band maximum of the fluorescence excitation spectrum of the CHTC-ME complex in aqueous solution. In this range, CHTC and especially ME show high photochemical stability. The nature of the radiation effect on the studied compounds in the hard UV range (λ < 330 nm) differs greatly from that in the range 330–750 nm. It is apparently accompanied by significant photochemical transmutations of all system components. By comparing the characteristics of the CHTC-ME systems with those of the related drug doxycycline (DC-ME), the conclusion has been made that the chlorine atom plays a vital role in formation of the short-wavelength band in the fluorescence spectrum of the CHTC-ME complex. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 1, pp. 52–62, January–February, 2008.     

Enhancement of fluorescence of porous silicon upon saturation by liquid crystal

The fluorescence of samples of porous silicon of various morphologies that are filled with a liquid crystal (LC), n-pentyl-n′-cyanobiphenyl (5CB), is studied. The fluorescence spectra of the sample, along with the long-wavelength band of porous silicon with a maximum in the range 627–667 nm, exhibit a short-wavelength band of 5CB with a maximum in the range 385–410 nm. The radiative relaxation times of porous silicon and 5CB lie in the micro- and nanosecond ranges, respectively. It is found that the filling of pores with 5CB enhances the fluorescence of porous silicon by two to three times. This enhancement is caused by non-radiative energy transfer from 5CB to the porous matrix as a result of efficient interactions between LC molecules and pore walls. Using IR spectroscopy, it is shown that the formation of hydrogen bonds between cyano groups of 5CB molecules and silanol groups of pore surface is the predominant type of these interactions. A transfer mechanism is suggested according to which excited associates of 5CB molecules transfer their energy via surface channels to excitons of porous silicon, enhancing its fluorescence.