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Sample records for absorption spectra fluorescence

  1. Theoretical investigations of absorption and fluorescence spectra of protonated pyrene.

    PubMed

    Chin, Chih-Hao; Lin, Sheng Hsien

    2016-05-25

    The equilibrium geometry and 75 vibrational normal-mode frequencies of the ground and first excited states of protonated pyrene isomers were calculated and characterized in the adiabatic representation by using the complete active space self-consistent field (CASSCF) method. Electronic absorption spectra of solid neon matrixes in the wavelength range 495-415 nm were determined by Maier et al. and they were analyzed using time-dependent density functional theory calculations (TDDFT). CASSCF calculations and absorption and emission spectra simulations by one-photon excitation equations were used to optimize the excited and ground state structures of protonated pyrene isomers. The absorption band was attributed to the S0 → S1 electronic transition in 1H-Py(+), and a band origin was used at 20580.96 cm(-1). The displaced harmonic oscillator approximation and Franck-Condon approximation were used to simulate the absorption spectrum of the (1) (1)A' ← X[combining tilde](1)A' transition of 1H-Py(+), and the main vibronic transitions were assigned for the first ππ* state. It shows that the vibronic structures were dominated by one of the eight active totally symmetric modes, with ν15 being the most crucial. This indicates that the electronic transition of the S1((1)A') state calculated in the adiabatic representation effectively includes a contribution from the adiabatic vibronic coupling through Franck-Condon factors perturbed by harmonic oscillators. The present method can adequately reproduce experimental absorption and fluorescence spectra of a gas phase. PMID:27181017

  2. Vibronic Structures in Absorption and Fluorescence Spectra of Firefly Oxyluciferin in Aqueous Solutions.

    PubMed

    Hiyama, Miyabi; Noguchi, Yoshifumi; Akiyama, Hidefumi; Yamada, Kenta; Koga, Nobuaki

    2015-01-01

    To elucidate the factors determining the spectral shapes and widths of the absorption and fluorescence spectra for keto and enol oxyluciferin and their conjugate bases in aqueous solutions, the intensities of vibronic transitions between their ground and first electronic excited states were calculated for the first time via estimation of the vibrational Franck-Condon factors. The major normal modes, overtones and combination tones in absorption and fluorescence spectra are similar for all species. The theoretical full widths at half maximum of absorption spectra are 0.4-0.7 eV and those for the fluorescence spectra are 0.4-0.5 eV, except for phenolate-keto that exhibits exceptionally sharp peak widths due to the dominance of the 0-0' or 0'-0 band. These spectral shapes and widths explain many relevant features of the experimentally observed spectra. PMID:25946599

  3. Fluorescence, Absorption, and Excitation Spectra of Polycyclic Aromatic Hydrocarbons as a Tool for Quantitative Analysis

    ERIC Educational Resources Information Center

    Rivera-Figueroa, A. M.; Ramazan, K. A.; Finlayson-Pitts, B. J.

    2004-01-01

    A quantitative and qualitative study of the interplay between absorption, fluorescence, and excitation spectra of pollutants called polycyclic aromatic hydrocarbons (PAHs) is conducted. The study of five PAH displays the correlation of the above-mentioned properties along with the associated molecular changes.

  4. Absorption and Fluorescence Spectra of Poly(p-phenylenevinylene) (PPV) Oligomers: An ab Initio Simulation

    PubMed Central

    2014-01-01

    The absorption and fluorescence spectra of poly(p-phenylenevinylene) (PPV) oligomers with up to seven repeat units were theoretically investigated using the algebraic diagrammatic construction method to second order, ADC(2), combined with the resolution-of-the-identity (RI) approach. The ground and first excited state geometries of the oligomers were fully optimized. Vertical excitation energies and oscillator strengths of the first four transitions were computed. The vibrational broadening of the absorption and fluorescence spectra was studied using a semiclassical nuclear ensemble method. After correcting for basis set and solvent effects, we achieved a balanced description of the absorption and fluorescence spectra by means of the ADC(2) approach. This fact is documented by the computed Stokes shift along the PPV series, which is in good agreement with the experimental values. The experimentally observed band width of the UV absorption and fluorescence spectra is well reproduced by the present simulations showing that the nuclear ensemble generated should be well suitable for consecutive surface hopping dynamics simulations. PMID:25415930

  5. Theoretical study of absorption and fluorescence spectra of firefly luciferin in aqueous solutions.

    PubMed

    Hiyama, Miyabi; Akiyama, Hidefumi; Yamada, Kenta; Koga, Nobuaki

    2012-01-01

    The absorption and fluorescence spectra of firefly luciferin, which is an analog of oxyluciferin, are investigated by performing the density functional theory (DFT) calculations, especially focusing on the experimentally unassigned peaks. Time-dependent DFT calculations are performed for the excited states of firefly luciferin and its conjugate acids and bases. We find that (1) the peaks in the experimental absorption spectra correspond to the excited states of not only (6'O(-), 4COO(-)) and (6'OH, 4COO(-)), but also (6'OH, 4COOH) and (6'OH, 3H(+), 4COOH); (2) the peaks in the experimental fluorescence spectra correspond to the excited states of not only (6'O(-), 4COO(-)), but also (6'OH, 4COO(-)), (6'O(-), 4COOH), (6'OH, 4COOH) and (6'OH, 3H(+), 4COOH); (3) the unassigned peak near 400 nm in the experimental absorption spectra at pH 1 is assigned to the absorption from the equilibrium ground state to the first excited state of (6'OH, 3H(+), 4COOH); and (4) the unassigned peak at 610 nm in the experimental fluorescence spectra corresponds to the transition from the equilibrium first excited state to the ground state of (6'OH, 4COO(-)). PMID:22364397

  6. [Study on the absorption and fluorescence spectra of ethylene glycol and glycerol].

    PubMed

    Xu, Hui; Zhu, Tuo; Yu, Rui-Peng

    2007-07-01

    The absorption and fluorescence spectra of ethylene glycol and glycerol solution induced by UV light were studied respectively in the present paper. The most intense absorption wavelength for both of them was located at 198 nm. Moreover, fluorescence was detected when induced by suitable UV light, and the corresponding fluorescence spectra were listed. But there is no obvious relationship found between the fluorescence intensity and the excited wavelength, and a further research should be done. From the first derivative fluorescence spectra of ethylene glycol, it was concluded that under the UV light of 210 nm, the variation speed for relative intensity proved to be the fastest. In contrast, when excited by 225 nm, the speed proved to be the slowest. In addition, based on the quantum calculation and the transition from HOMO to LUMO of electronics in one-dimensional quantum well, the authors attempted to give out the value of absorption wavelength. In consideration of the bond-length variety brought out by the chain processing, the error between the experimental and calculation values should be apprehensible, and the latter can serve as some reference value in theory.

  7. Orthogonal spectra and cross sections: Application to optimization of multi-spectral absorption and fluorescence lidar

    SciTech Connect

    Shokair, I.R.

    1997-09-01

    This report addresses the problem of selection of lidar parameters, namely wavelengths for absorption lidar and excitation fluorescence pairs for fluorescence lidar, for optimal detection of species. Orthogonal spectra and cross sections are used as mathematical representations which provide a quantitative measure of species distinguishability in mixtures. Using these quantities, a simple expression for the absolute error in calculated species concentration is derived and optimization is accomplished by variation of lidar parameters to minimize this error. It is shown that the optimum number of wavelengths for detection of a species using absorption lidar (excitation fluorescence pairs for fluorescence lidar) is the same as the number of species in the mixture. Each species present in the mixture has its own set of optimum wavelengths. There is usually some overlap in these sets. The optimization method is applied to two examples, one using absorption and the other using fluorescence lidar, for analyzing mixtures of four organic compounds. The effect of atmospheric attenuation is included in the optimization process. Although the number of optimum wavelengths might be small, it is essential to do large numbers of measurements at these wavelengths in order to maximize canceling of statistical errors.

  8. Absorption, fluorescence, and Raman spectra of mass-selected rhenium dimers in argon matrices

    NASA Astrophysics Data System (ADS)

    Hu, Zhendong; Dong, Jian-Guo; Lombardi, John R.; Lindsay, D. M.; Harbich, W.

    1994-07-01

    We report absorption, laser fluorescence, and Raman spectra for Re2 in an argon matrix prepared by the mass-selected ion deposition technique. The dirhenium absorption spectrum consists of seven band systems (A-G) extending from the near infrared into the ultraviolet region. For the A system (a simple vibrational progression), we find T0=10 817(1) cm-1, ωe=317.1(5) cm-1 and ωexe=1.0(1) cm-1. A Franck-Condon analysis of the A system intensities predicts that this state has a smaller equilibrium internuclear distance than the ground state (Δre=-0.073 Å), in violation of Badger's rule. The B system starts at 13 250 cm-1 and consists of four overlapping (and possibly perturbed) subsystems, whose average vibrational spacing is 270(11) cm-1. The C, D, E, and F systems (vibrational spacings in parentheses) are centered at 22 300 cm-1 (210 cm-1), 24 500 cm-1 (195 cm-1), 29 150 cm-1 (175 cm-1), and 32 900 cm-1 (160 cm-1), respectively. Weak fluorescence spectra, obtained upon laser excitation into the A system, were characterized by vibrational progressions to the dimer ground (X) state and to a low lying (X') state for which T0=357.6(5) cm-1 and ωe=332.3(2) cm-1. Raman and fluorescence progressions to the ground state were observed when the B system was excited. These data give ωe=337.9(49) cm-1 for the dimer ground state in good agreement with measurements from photodetachment spectra [J. Am. Chem. Soc. 108, 178 (1986)]. We propose likely assignments for the low lying electronic states of Re2 and discuss our results in terms of the bonding in the other group VIIB dimers, Mn2 and Tc2.

  9. Two-photon fluorescence absorption and emission spectra of dyes relevant for cell imaging.

    PubMed

    Bestvater, F; Spiess, E; Stobrawa, G; Hacker, M; Feurer, T; Porwol, T; Berchner-Pfannschmidt, U; Wotzlaw, C; Acker, H

    2002-11-01

    Two-photon absorption and emission spectra for fluorophores relevant in cell imaging were measured using a 45 fs Ti:sapphire laser, a continuously tuneable optical parametric amplifier for the excitation range 580-1150 nm and an optical multichannel analyser. The measurements included DNA stains, fluorescent dyes coupled to antibodies as well as organelle trackers, e.g. Alexa and Bodipy dyes, Cy2, Cy3, DAPI, Hoechst 33342, propidium iodide, FITC and rhodamine. In accordance with the two-photon excitation theory, the majority of the investigated fluorochromes did not reveal significant discrepancies between the two-photon and the one-photon emission spectra. However, a blue-shift of the absorption maxima ranging from a few nanometres up to considerably differing courses of the spectrum was found for most fluorochromes. The potential of non-linear laser scanning fluorescence microscopy is demonstrated here by visualizing multiple intracellular structures in living cells. Combined with 3D reconstruction techniques, this approach gives a deeper insight into the spatial relationships of subcellular organelles. PMID:12423261

  10. Shape of the absorption and fluorescence spectra of condensed phases and transition energies.

    PubMed

    Lagos, Miguel; Paredes, Rodrigo

    2014-11-13

    General integral expressions for the temperature-dependent profile of the spectral lines of photon absorption and emission by atomic or molecular species in a condensed environment are derived with no other hypothesis than: (a) The acoustic vibrational modes of the condensed host medium constitute the thermodynamic energy reservoir at a given constant temperature, and local electronic transitions modifying the equilibrium configuration of the surroundings are multiphonon events, regardless of the magnitude of the transition energy. (b) Electron-phonon coupling is linear in the variations of the bond length. The purpose is to develop a theoretical tool for the analysis of the spectra, allowing us to grasp highly accurate information from fitting the theoretical line shape function to experiment, including those spectra displaying wide features. The method is illustrated by applying it to two dyes, Lucifer Yellow CH and Coumarin 1, which display fluorescence maxima of 0.41 and 0.51 eV fwhm. Fitting the theoretical curves to the spectra indicates that the neat excitation energies are 2.58 eV ± 2.5% and 3.00 eV ± 2.0%, respectively.

  11. pH-Induced changes in electronic absorption and fluorescence spectra of phenazine derivatives

    NASA Astrophysics Data System (ADS)

    Ryazanova, O. A.; Voloshin, I. M.; Makitruk, V. L.; Zozulya, V. N.; Karachevtsev, V. A.

    2007-04-01

    The visible electronic absorption and fluorescence spectra as well as fluorescence polarization degrees of imidazo-[4,5-d]-phenazine (F1), 2-methylimidazo-[4,5-d]-phenazine (F2), 2-trifluoridemethylimidazo-[4,5-d]-phenazine (F3), 1,2,3-triazole-[4,5-d]-phenazine (F4) and their glycosides, imidazo-[4,5-d]-phenazine-N1-β- D-ribofuranoside (F1rib), 1,2,3-triazole-[4,5-d]-phenazine-N1-β- D-glucopyranoside (F4gl), were investigated in aqueous buffered solutions over the pH range of 0-12, where the spectral transformations were found to be reversible. The effects of protonation and deprotonation on spectral properties of these dyes were studied. We have determined the ranges of pH, where individual ionic species are predominant. In aqueous buffered solutions the fluorescence was found only for neutral species of F1, F1rib, F2, and F4gl dyes, whereas for the ionic forms of these dyes, as well as for F3 and F4 ones, the fluorescence has not been detected. The concentrational deprotonation p Ka values were evaluated from experimental data. It was shown that donor-acceptor properties of the substituent group in the second position of the pentagonal ring substantially affect the values of the deprotonation constants and the character of protonation for chromophore. The substitution of a hydrogen atom in the NH-group by the sugar residue blocks the formation of the anionic species, and results in enhancement of the dye emission intensity. The steep emission dependence for F1 and F1rib over pH range of 0-7 with intensities ratio of IpH 7/ IpH 1 = 60 allows us to propose them as possible indicator dyes in luminescence based pH sensors for investigation of processes accompanied by acidification, e.g. as gastric pH-sensors. A comparative analysis of the studied dyes has shown that F4gl is the most promising compound to be used as a fluorescent probe for investigation of molecular hybridization of nucleic acids.

  12. Vibrationally Resolved Absorption and Fluorescence Spectra of Firefly Luciferin: A Theoretical Simulation in the Gas Phase and in Solution.

    PubMed

    Cheng, Yuan-Yuan; Liu, Ya-Jun

    2016-07-01

    Firefly bioluminescence has been applied in several fields. However, the absorption and fluorescence spectra of the substrate, luciferin, have not been observed at the vibrational level. In this study, the vibrationally resolved absorption and fluorescence spectra of firefly luciferin (neutral form LH2 , phenolate ion form LH(-) and dianion form L(2-) ) are simulated using the density functional method and convoluted by a Gaussian function, with displacement, distortion and Duschinsky effects in the framework of the Franck-Condon approximation. Both neutral and anionic forms of the luciferin are considered in the gas phase and in solution. The simulated spectra have desired band maxima with the experimental ones. The vibronic structure analysis reveals that the features of the most contributive vibrational modes coincide with the key geometry-changing region during transition between the ground state and the first singlet excited state. PMID:27165852

  13. Solvent dependence of two-photon absorption spectra of the enhanced green fluorescent protein (eGFP) chromophore

    NASA Astrophysics Data System (ADS)

    Hosoi, Haruko; Tayama, Ryo; Takeuchi, Satoshi; Tahara, Tahei

    2015-06-01

    Two-photon absorption spectra of 4‧-hydroxybenzylidene-2,3-dimethylimidazolinone, a model chromophore of enhanced green fluorescent protein (eGFP), were measured in various solvents. The two-photon absorption band of its anionic form is markedly blue-shifted from the corresponding one-photon absorption band in all solvents. Moreover, the magnitude of the blue shift varies largely depending on the solvent, which does not accord with the assignment of the two-photon absorption band to the transitions to the vibrationally excited S1 state. Our finding is readily rationalized by considering overlapping contributions of the S1 ← S0 and S2 ← S0 transitions, suggesting the involvement of the S2 state also in two-photon fluorescence of eGFP.

  14. Study on the interaction between fluoroquinolones and erythrosine by absorption, fluorescence and resonance Rayleigh scattering spectra and their application

    NASA Astrophysics Data System (ADS)

    Wang, Jian; Liu, Zhongfang; Liu, Jiangtao; Liu, Shaopu; Shen, Wei

    2008-03-01

    In pH 4.4-4.5 Britton-Robinson (BR) buffer solution, fluoroquinolone antibiotics (FLQs) including ciprofloxacin (CIP), norfloxacin (NOR), levofloxacin (LEV) and lomefloxacin (LOM) could react with erythrosine (Ery) to form 1:1 ion-association complexes, which not only resulted in the changes of the absorption spectra and the quenching of fluorescence, but also resulted in the great enhancement of resonance Rayleigh scattering (RRS). These offered some indications of the determination of fluoroquinolone antibiotics by spectrophotometric, fluorescence and resonance Rayleigh scattering methods. The detection limits for fluoroquinolone antibiotics were in the range of 0.097-0.265 μg/mL for absorption methods, 0.022-0.100 μg/mL for fluorophotometry and 0.014-0.027 μg/mL for RRS method, respectively. Among them, the RRS method had the highest sensitivity. In this work, the spectral characteristics of the absorption, fluorescence and RRS, the optimum conditions of the reactions and the properties of the analytical chemistry were investigated. The methods have been successfully applied to determination of some fluoroquinolone antibiotics in human urine samples and tablets. Taking CIP-Ery system as an example, the charge distribution, the enthalpy of formation and the mean polarizability were calculated by density function theory (DFT) method. In addition, the reasons for the enhancement of scattering spectra were discussed.

  15. Effects of annealing treatment and gamma irradiation on the absorption and fluorescence spectra of Cr:GSGG laser crystal

    NASA Astrophysics Data System (ADS)

    Sun, D. L.; Luo, J. Q.; Xiao, J. Z.; Zhang, Q. L.; Jiang, H. H.; Yin, S. T.; Wang, Y. F.; Ge, X. W.

    2008-09-01

    The influence of annealing treatments and gamma-ray irradiation on the absorption and fluorescence spectra of Cr:GSGG crystals grown by the Czochralski method has been investigated. Two absorption bands located near 686 nm and 1050 nm were weakened markedly after the crystal was re-annealed in H2 atmosphere, which is due to the Cr4+ ions being de-oxidized into Cr3+ ions. The other two weak additional absorption bands induced by gamma-ray irradiation appearing near 310 nm and 480 nm are ascribed to the Fe2+ ions and F-type color centers, respectively. In particular, the gamma-ray irradiation with a dose of 100 Mrad has an effect of improving slightly the luminescence properties of Cr:GSGG crystals. The improvement mechanism is analyzed and discussed.

  16. New aspects concerning the energy transfer in carotenoids by measuring intracavity absorption spectra and delayed fluorescence

    NASA Astrophysics Data System (ADS)

    Bettermann, Hans; Bouschen, Werner; Ulrich, Lars; Domnick, Gabriele; Martin, H. D.

    1999-05-01

    The first excited singlet state and the lower energetic triplet states of carotenoids are considered to be involved in the light-harvesting as well as in the photochemical protection of cells, respectively. For this reason, the symmetry-forbidden S 0-S 1 (1 1A g-2 1A g) transitions and the multiplicity-forbidden S 0-T 2 (1 1A g-2 3A g) transition of the model carotenoid 8,13-dimethyl-2,2,19,19-tetramethoxy-icosa-4,6,8,10,12,14,16-heptaene-3,18-dione were investigated by intracavity absorption spectroscopy from low-concentrated ethanolic solutions. Both transitions are shaped by promoting modes caused by Herzberg-Teller coupling and the sequence of these modes allows the precise determination of the non-visible S 0-S 1 (0-0)- and S 0-T 2 (0-0)-transitions. The assignments of the singlet-triplet transitions were additionally supported by measuring delayed fluorescence from crystalline samples by directly exciting vibronic triplet states. The vibronic coupling is promoted by C-H bending vibrations of the chain and mainly by deformation modes of the terminating groups of the carotenoid.

  17. Solvents effect on the absorption and fluorescence spectra of 7-diethylamino-3-thenoylcoumarin: Evaluation and correlation between solvatochromism and solvent polarity parameters

    NASA Astrophysics Data System (ADS)

    Basavaraja, Jana; Inamdar, S. R.; Suresh Kumar, H. M.

    2015-02-01

    Effect of solvents of varying polarities on absorption and fluorescence spectra and dipole moment of laser dye: 7-diethylamino-3-thenoylcoumarin (DETC) has been investigated. A small band shift is obtained in the absorption spectra compared to emission spectra. The spectral shifts were correlated with Catalan's parameters using linear solvation energy relationship. It reveals that non-specific interaction measured by solvent polarity has more influence on absorption and solvent dipolarity contribution is significant in case of fluorescence. A bathochromic shift observed in absorption and emission spectra with increasing solvent polarity, which implied that the transition involved is π → π∗. The solvatochromic correlations were used to estimate the excited state dipole moment using experimentally determined ground state dipole moment. The observed single-state excited state dipole moment is found to be greater than the ground state.

  18. Solvent Effects on the Electronic Absorption and Fluorescence Spectra of HNP: Estimation of Ground and Excited State Dipole Moments.

    PubMed

    Desai, Vani R; Hunagund, Shirajahammad M; Basanagouda, Mahantesha; Kadadevarmath, Jagadish S; Sidarai, Ashok H

    2016-07-01

    We report the effect of solvents on absorption and fluorescence spectra of biologically active 3(2H)-pyridazinone namely 5-(2-hydroxy-naphthalen-1-yl)-2-phenyl-2H-pyridazin-3-one (HNP) in different solvents at room temperature. The ground and the excited state dipole moments of HNP molecule was estimated from Lippert's, Bakshiev's and Kawski-Chamma-Viallet's equations using the solvatochromic shift method. The ground state dipole moment (μ g ) was also estimated by Guggenheim and Higasi method using the dielectric constant and refractive index of solute at different concentrations, the μ g value obtained from these two methods are comparable to the μ g value obtained by the solvatochromic shift method. The excited state dipole moment (μ e ) is greater than the ground state dipole moment (μ g ), which indicates that the excited state is more polar than the ground state. Further, we have evaluated the change in dipole moment (Δμ) from the solvatochromic shift method and on the basis of molecular-microscopic solvent polarity parameter[Formula: see text], later on the values were compared. PMID:27220623

  19. Ultrafast Time-Resolved Emission and Absorption Spectra of meso-Pyridyl Porphyrins upon Soret Band Excitation Studied by Fluorescence Up-Conversion and Transient Absorption Spectroscopy.

    PubMed

    Venkatesh, Yeduru; Venkatesan, M; Ramakrishna, B; Bangal, Prakriti Ranjan

    2016-09-01

    A comprehensive study of ultrafast molecular relaxation processes of isomeric meso-(pyridyl) porphyrins (TpyPs) has been carried out by using femtosecond time-resolved emission and absorption spectroscopic techniques upon pumping at 400 nm, Soret band (B band or S2), in 4:1 dichloromethane (DCM) and tetrahydrofuran (THF) solvent mixture. By combined studies of fluorescence up-conversion, time-correlated single photon counting, and transient absorption spectroscopic techniques, a complete model with different microscopic rate constants associated with elementary processes involved in electronic manifolds has been reported. Besides, a distinct coherent nuclear wave packet motion in Qy state is observed at low-frequency mode, ca. 26 cm(-1) region. Fluorescence up-conversion studies constitute ultrafast time-resolved emission spectra (TRES) over the whole emission range (430-710 nm) starting from S2 state to Qx state via Qy state. Careful analysis of time profiles of up-converted signals at different emission wavelengths helps to reveal detail molecular dynamics. The observed lifetimes are as indicated: A very fast decay component with 80 ± 20 fs observed at ∼435 nm is assigned to the lifetime of S2 (B) state, whereas being a rise component in the region of between 550 and 710 nm emission wavelength pertaining to Qy and Qx states, it is attributed to very fast internal conversion (IC) occurring from B → Qy and B → Qx as well. Two distinct components of Qy emission decay with ∼200-300 fs and ∼1-1.5 ps time constants are due to intramolecular vibrational redistribution (IVR) induced by solute-solvent inelastic collisions and vibrational redistribution induced by solute-solvent elastic collision, respectively. The weighted average of these two decay components is assigned as the characteristic lifetime of Qy, and it ranges between 0.3 and 0.5 ps. An additional ∼20 ± 2 ps rise component is observed in Qx emission, and it is assigned to the formation time of

  20. Ultrafast Time-Resolved Emission and Absorption Spectra of meso-Pyridyl Porphyrins upon Soret Band Excitation Studied by Fluorescence Up-Conversion and Transient Absorption Spectroscopy.

    PubMed

    Venkatesh, Yeduru; Venkatesan, M; Ramakrishna, B; Bangal, Prakriti Ranjan

    2016-09-01

    A comprehensive study of ultrafast molecular relaxation processes of isomeric meso-(pyridyl) porphyrins (TpyPs) has been carried out by using femtosecond time-resolved emission and absorption spectroscopic techniques upon pumping at 400 nm, Soret band (B band or S2), in 4:1 dichloromethane (DCM) and tetrahydrofuran (THF) solvent mixture. By combined studies of fluorescence up-conversion, time-correlated single photon counting, and transient absorption spectroscopic techniques, a complete model with different microscopic rate constants associated with elementary processes involved in electronic manifolds has been reported. Besides, a distinct coherent nuclear wave packet motion in Qy state is observed at low-frequency mode, ca. 26 cm(-1) region. Fluorescence up-conversion studies constitute ultrafast time-resolved emission spectra (TRES) over the whole emission range (430-710 nm) starting from S2 state to Qx state via Qy state. Careful analysis of time profiles of up-converted signals at different emission wavelengths helps to reveal detail molecular dynamics. The observed lifetimes are as indicated: A very fast decay component with 80 ± 20 fs observed at ∼435 nm is assigned to the lifetime of S2 (B) state, whereas being a rise component in the region of between 550 and 710 nm emission wavelength pertaining to Qy and Qx states, it is attributed to very fast internal conversion (IC) occurring from B → Qy and B → Qx as well. Two distinct components of Qy emission decay with ∼200-300 fs and ∼1-1.5 ps time constants are due to intramolecular vibrational redistribution (IVR) induced by solute-solvent inelastic collisions and vibrational redistribution induced by solute-solvent elastic collision, respectively. The weighted average of these two decay components is assigned as the characteristic lifetime of Qy, and it ranges between 0.3 and 0.5 ps. An additional ∼20 ± 2 ps rise component is observed in Qx emission, and it is assigned to the formation time of

  1. Monomeric C-phycocyanin at room temperature and 77 K. Resolution of the absorption and fluorescence spectra of the individual chromophores and the energy-transfer rate constants

    SciTech Connect

    Debreczeny, M.P.; Sauer, K. Univ. of California, Berkeley, CA ); Zhou, J.; Bryant, D.A. )

    1993-09-23

    At both room temperature (RT) and 77 K, the absorption and fluorescence spectra of the three individual chromophore types ([alpha][sub 84], [beta][sub 84], and [beta][sub 155]) found in monomeric C-phycocyanin ([alpha][sup PC][beta][sup PC]), isolated from the cyanobacterium Synechococcus sp. PCC 7002, were resolved along with the rates of energy transfer between the chromophores. The cpcB/C155S mutant, whose PC is missing the [beta][sub 155] chromophore, was useful in effecting this resolution. At RT, the single broad peak in the visible region of the absorption spectrum of ([alpha][sup PC][beta][sup PC]) was resolved into its three-component spectra by comparing the steady-state absorption spectra of the isolated wild-type [alpha] subunit of PC ([alpha][sup PC]) (containing only the [alpha][sub 84] chromophore) with those of the monomeric PCs isolated from the mutant strain ([alpha][sup PC][beta]*) and the wild-type strain ([alpha][sup PC][beta][sup PC]). At 77 K, the visible region of the absorption spectrum of ([alpha][sup PC][beta][sup PC]) splits into two peaks. This partial resolution at 77 K of the chromophore spectra of ([alpha][sup PC][beta][sup PC]) when compared with the 77 K absorption spectra of [alpha][sup PC], [beta][sup PC], and ([alpha][sup PC][beta]*) provided a confirmation of our RT assignments of the chromophore absorption spectra. 38 refs., 9 figs., 6 tabs.

  2. meso-(4-(N,N-dialkylamino)phenyl)-substituted subporphyrins: remarkably perturbed absorption spectra and enhanced fluorescence by intramolecular charge transfer interactions.

    PubMed

    Inokuma, Yasuhide; Easwaramoorthi, Shanmugam; Yoon, Zin Seok; Kim, Dongho; Osuka, Atsuhiro

    2008-09-17

    A series of meso-(4-(N,N-dibenzylamino)phenyl)-substituted subporphyrins was synthesized by means of Buchwald-Hartwig amination protocol. Substitution of the amino group at the 4-position of the meso-phenyl substituent resulted in a remarkable red shift in the absorption spectra and drastic enhancement of fluorescence intensity probably as a consequence of intramolecular CT interaction. These characteristics have been utilized to construct a cation-sensing system by appending a 1-aza-15-crown-5 unit to subporphyrin that displays large spectral changes upon cation binding.

  3. Calculation and interpretation of vibronic absorption and fluorescence spectra of the first electronic nπ* transitions of pyridine and pyrimidine

    NASA Astrophysics Data System (ADS)

    Ten, G. N.; Kadrov, D. M.; Berezin, M. K.; Baranov, V. I.

    2014-11-01

    We have calculated vibronic spectra of the first electronic nπ* transitions of pyridine and pyrimidine in the isolated state using the DFT method in the Franck-Condon approximation. Vibrational spectra for the ground and excited states have been calculated in the anharmonic approximation, which allowed us to refine the assignment of normal vibrations of pyridine and pyrimidine. We have done a complete interpretation of the vibrational structure of the absorption and fluorescence spectra of pyridine and pyrimidine. It has been shown that Fermi resonances between fundamental and combination vibrations and overtones 12 and 16 b + 4, 6 a and 2 × 16 b affect the formation of the vibrational structure of electronic spectra of pyrimidine. Good agreement between calculated and experimental spectra confirms the correctness of the models of the two molecules in their ground and excited states, which makes it possible to use the models in further investigations of various properties of these molecules in electronically excited states, e.g., tautomerism of pyrimidine bases of nucleic acids.

  4. [Characteristics of absorption and fluorescence spectra of dissolved organic matter from confluence of rivers: case study of Qujiang River-Jialing River and Fujiang River-Jialing River].

    PubMed

    Yan, Jin-Long; Jiang, Tao; Gao, Jie; Wei, Shi-Qiang; Lu, Song; Liu, Jiang

    2015-03-01

    Three-dimensional fluorescence spectroscopy combined with ultraviolet-visible (UV-Vis) absorption spectra was used to investigate the change characteristics of dissolved organic matter (DOM) in confluences water of Qujiang River-Jialing River and Fujiang River-Jialing River, respectively. The results suggested that DOM showed a significant terrestrial input signal in all the sampling sites, FI < 1.4, HIX > 0.8, possibly representing remarkable signals of humus resulted from humic-like component. Moreover, the mixing zone of this study showed a non-conservative mixed behavior, which had a limited contribution, and was not the dominant factor to interpret the change characteristics of DOM in confluences zones. Different land-use types along all the rivers had an obvious impact on DOM inputs. Results of cluster analysis showed that a higher degree of aromaticity and humification components was observed as the predominant contributor to DOM when the land-use type was forest and farmland ecosystem, for example the confluences of Qujiang River-Jialing River. On the other hand, high concentrations of DOM with relative simple structures were found in the water when the urban land-use type was predominant, for example the confluences of Fujiang River-Jialing River. Meanwhile, a new fluorescent signal of protein-like components (peak T) appeared, which manifested a significant effect on the water quality resulted from anthropogenic activities. PMID:25929053

  5. [Characteristics of absorption and fluorescence spectra of dissolved organic matter from confluence of rivers: case study of Qujiang River-Jialing River and Fujiang River-Jialing River].

    PubMed

    Yan, Jin-Long; Jiang, Tao; Gao, Jie; Wei, Shi-Qiang; Lu, Song; Liu, Jiang

    2015-03-01

    Three-dimensional fluorescence spectroscopy combined with ultraviolet-visible (UV-Vis) absorption spectra was used to investigate the change characteristics of dissolved organic matter (DOM) in confluences water of Qujiang River-Jialing River and Fujiang River-Jialing River, respectively. The results suggested that DOM showed a significant terrestrial input signal in all the sampling sites, FI < 1.4, HIX > 0.8, possibly representing remarkable signals of humus resulted from humic-like component. Moreover, the mixing zone of this study showed a non-conservative mixed behavior, which had a limited contribution, and was not the dominant factor to interpret the change characteristics of DOM in confluences zones. Different land-use types along all the rivers had an obvious impact on DOM inputs. Results of cluster analysis showed that a higher degree of aromaticity and humification components was observed as the predominant contributor to DOM when the land-use type was forest and farmland ecosystem, for example the confluences of Qujiang River-Jialing River. On the other hand, high concentrations of DOM with relative simple structures were found in the water when the urban land-use type was predominant, for example the confluences of Fujiang River-Jialing River. Meanwhile, a new fluorescent signal of protein-like components (peak T) appeared, which manifested a significant effect on the water quality resulted from anthropogenic activities.

  6. Estimation of ground and excited state dipole moment of laser dyes C504T and C521T using solvatochromic shifts of absorption and fluorescence spectra

    NASA Astrophysics Data System (ADS)

    Basavaraja, Jana; Suresh Kumar, H. M.; Inamdar, S. R.; Wari, M. N.

    2016-02-01

    The absorption and fluorescence spectra of laser dyes: coumarin 504T (C504T) and coumarin 521T (C521T) have been recorded at room temperature in a series of non-polar and polar solvents. The spectra of these dyes showed bathochromic shift with increasing in solvent polarity indicating the involvement of π → π* transition. Kamlet-Taft and Catalan solvent parameters were used to analyze the effect of solvents on C504T and C521T molecules. The study reveals that both general solute-solvent interactions and specific interactions are operative in these two systems. The ground state dipole moment was estimated using Guggenheim's method and also by quantum mechanical calculations. The solvatochromic data were used to determine the excited state dipole moment (μe). It is observed that dipole moment value of excited state (μe) is higher than that of the ground state in both the laser dyes indicating that these dyes are more polar in nature in the excited state than in the ground state.

  7. Fluorescence excitation and ultraviolet absorption spectra and theoretical calculations for benzocyclobutane: Vibrations and structure of its excited S{sub 1}(π,π{sup *}) electronic state

    SciTech Connect

    Shin, Hee Won; Ocola, Esther J.; Laane, Jaan; Kim, Sunghwan

    2014-01-21

    The fluorescence excitation spectra of jet-cooled benzocyclobutane have been recorded and together with its ultraviolet absorption spectra have been used to assign the vibrational frequencies for this molecule in its S{sub 1}(π,π{sup *}) electronic excited state. Theoretical calculations at the CASSCF(6,6)/aug-cc-pVTZ level of theory were carried out to compute the structure of the molecule in its excited state. The calculated structure was compared to that of the molecule in its electronic ground state as well as to the structures of related molecules in their S{sub 0} and S{sub 1}(π,π{sup *}) electronic states. In each case the decreased π bonding in the electronic excited states results in longer carbon-carbon bonds in the benzene ring. The skeletal vibrational frequencies in the electronic excited state were readily assigned and these were compared to the ground state and to the frequencies of five similar molecules. The vibrational levels in both S{sub 0} and S{sub 1}(π,π{sup *}) states were remarkably harmonic in contrast to the other bicyclic molecules. The decreases in the frequencies of the out-of-plane skeletal modes reflect the increased floppiness of these bicyclic molecules in their S{sub 1}(π,π{sup *}) excited state.

  8. Interactions of cyanine dyes with nucleic acids. XXIV. Aggregation of monomethine cyanine dyes in presence of DNA and its manifestation in absorption and fluorescence spectra

    NASA Astrophysics Data System (ADS)

    Ogul'chansky, T. Yu; Losytskyy, M. Yu; Kovalska, V. B.; Yashchuk, V. M.; Yarmoluk, S. M.

    2001-06-01

    Absorption, fluorescence emission and excitation spectra of benzothiazole cyanine dyes — thiazole orange (TO) and 7-methyl-6-(3-methyl-2,3-dihydro-1,3-benzothiazol-2-ylidenmethyl) [1,3] dioxolo [4',5':4,5] benzo [d] [1,3] thiazolium methylmethosulfate (Cyan 13) — were investigated over a wide concentration range. The dyes form aggregates with a 'sandwich'-like structure in water solution. At low dye to DNA concentrations ratios, Cyan 13 and TO monomers appear to interact with the DNA. On increasing the dye to DNA concentrations ratio, free dye molecules aggregate with the DNA-bound ones. The spectra of the free dye aggregates and the aggregates formed on the DNA, are characterized by an anomalously large (more than 100 nm) Stokes shift. This suggests, that the π-electron systems of the aggregates undergo substantial changes in excited state, compared to those of the monomers. The formation of aggregates consisting of the free and DNA-bound dye molecules can be explained using the half-intercalation model of the interaction of the cyanine dye monomers with the DNA.

  9. Absorption and fluorescence spectroscopy on a smartphone

    NASA Astrophysics Data System (ADS)

    Hossain, Md. Arafat; Canning, John; Cook, Kevin; Ast, Sandra; Rutledge, Peter J.; Jamalipour, Abbas

    2015-07-01

    A self-powered smartphone-based field-portable "dual" spectrometer has been developed for both absorption and fluorescence measurements. The smartphone's existing flash LED has sufficient optical irradiance to undertake absorption measurements within a 3D-printed case containing a low cost nano-imprinted polymer diffraction grating. A UV (λex ~ 370 nm) and VIS (λex ~ 450 nm) LED are wired into the circuit of the flash LED to provide an excitation source for fluorescence measurements. Using a customized app on the smartphone, measurements of absorption and fluorescence spectra are demonstrated using pH-sensitive and Zn2+-responsive probes. Detection over a 300 nm span with 0.42 nm/pixel spectral resolution is demonstrated. Despite the low cost and small size of the portable spectrometer, the results compare well with bench top instruments.

  10. Franck-Condon factors perturbed by damped harmonic oscillators: Solvent enhanced X {sup 1}A{sub g} ↔ A{sup 1}B{sub 1u} absorption and fluorescence spectra of perylene

    SciTech Connect

    Wang, Chen-Wen; Zhu, Chaoyuan Lin, Sheng-Hsien; Yang, Ling; Yu, Jian-Guo

    2014-08-28

    Damped harmonic oscillators are utilized to calculate Franck-Condon factors within displaced harmonic oscillator approximation. This is practically done by scaling unperturbed Hessian matrix that represents local modes of force constants for molecule in gaseous phase, and then by diagonalizing perturbed Hessian matrix it results in direct modification of Huang–Rhys factors which represent normal modes of solute molecule perturbed by solvent environment. Scaling parameters are empirically introduced for simulating absorption and fluorescence spectra of an isolated solute molecule in solution. The present method is especially useful for simulating vibronic spectra of polycyclic aromatic hydrocarbon molecules in which hydrogen atom vibrations in solution can be scaled equally, namely the same scaling factor being applied to all hydrogen atoms in polycyclic aromatic hydrocarbons. The present method is demonstrated in simulating solvent enhanced X {sup 1}A{sub g} ↔ A{sup 1}B{sub 1u} absorption and fluorescence spectra of perylene (medium-sized polycyclic aromatic hydrocarbon) in benzene solution. It is found that one of six active normal modes v{sub 10} is actually responsible to the solvent enhancement of spectra observed in experiment. Simulations from all functionals (TD) B3LYP, (TD) B3LYP35, (TD) B3LYP50, and (TD) B3LYP100 draw the same conclusion. Hence, the present method is able to adequately reproduce experimental absorption and fluorescence spectra in both gas and solution phases.

  11. Environments of the four tryptophans in the extracellular domain of human tissue factor: comparison of results from absorption and fluorescence difference spectra of tryptophan replacement mutants with the crystal structure of the wild-type protein.

    PubMed Central

    Hasselbacher, C A; Rusinova, E; Waxman, E; Rusinova, R; Kohanski, R A; Lam, W; Guha, A; Du, J; Lin, T C; Polikarpov, I

    1995-01-01

    The local environments of the four tryptophan residues of the extracellular domain of human tissue factor (sTF) were assessed from difference absorption and fluorescence spectra. The difference spectra were derived by subtracting spectra from single Trp-to-Phe or Trp-to-Tyr replacement mutants from the corresponding spectrum of the wild-type protein. Each of the mutants was capable of enhancing the proteolytic activity of factor VIIa showing that the mutations did not introduce major structural changes, although the mutants were more susceptible to denaturation by guanidinium chloride. The difference spectra indicate that the Trp residues are buried to different extents within the protein matrix. This evaluation was compared with the x-ray crystal structure of sTF. There is excellent agreement between predictions from the difference spectra and the environments of the Trp residues observed in the x-ray crystal structure, demonstrating that difference absorption and particularly fluorescence spectra derived from functional single-Trp replacement mutants can be used to obtain information about the local environments of individual Trp residues in multi-tryptophan proteins. Images FIGURE 7 FIGURE 8 PMID:7669897

  12. [Saltation behavior in excitation spectra of fluorescent molecules].

    PubMed

    Miao, Di; Xu, Yi-zhuang; Yang, Jun; Xu, Zhen-hua; Wu, Jin-guang

    2004-05-01

    Excitation spectra are commonly used to study relationship between molecular structure of fluorescent substances and energy transfer during the fluorescence process. It is generally taken for granted that the excitation spectrum of the sample is equivalent to its absorption spectrum, even a copy of the latter. However, exceptions have been found in many cases. Considering various factors that affect the excitation spectra of solution comprehensively, a model has been established to study the behavior of the excitation spectra. After analyzing the model mathematically, including introducing catastrophe theory, we came into the following conclusions: As far as the topological properties are concerned, the excitation spectra are the same as its absorption spectra, provided the concentration of the substance is below a threshold. However, when the concentration is beyond the threshold, the excitation spectra undergo a series of topological saltation, leading to significant a deviation from the absorption spectra. Comparative studies of both excitation and absorption spectra of naphthalene dissolved in n-hexane confirmed the above hypothesis.

  13. Theoretical study on absorption and emission spectra of adenine analogues.

    PubMed

    Liu, Hongxia; Song, Qixia; Yang, Yan; Li, Yan; Wang, Haijun

    2014-04-01

    Fluorescent nucleoside analogues have attracted much attention in studying the structure and dynamics of nucleic acids in recent years. In the present work, we use theoretical calculations to investigate the structural and optical properties of four adenine analogues (termed as A1, A2, A3, and A4), and also consider the effects of aqueous solution and base pairing. The results show that the fluorescent adenine analogues can pair with thymine to form stable H-bonded WC base pairs. The excited geometries of both adenine analogues and WC base pairs are similar to the ground geometries. The absorption and emission maxima of adenine analogues are greatly red shifted compared with nature adenine, the oscillator strengths of A1 and A2 are stronger than A3 and A4 in both absorption and emission spectra. The calculated low-energy peaks in the absorption spectra are in good agreement with the experimental data. In general, the aqueous solution and base pairing can slightly red-shift both the absorption and emission maxima, and can increase the oscillator strengths of absorption spectra, but significantly decrease the oscillator strengths of A3 in emission spectra.

  14. Creating semiconductor metafilms with designer absorption spectra.

    PubMed

    Kim, Soo Jin; Fan, Pengyu; Kang, Ju-Hyung; Brongersma, Mark L

    2015-01-01

    The optical properties of semiconductors are typically considered intrinsic and fixed. Here we leverage the rapid developments in the field of optical metamaterials to create ultrathin semiconductor metafilms with designer absorption spectra. We show how such metafilms can be constructed by placing one or more types of high-index semiconductor antennas into a dense array with subwavelength spacings. It is argued that the large absorption cross-section of semiconductor antennas and their weak near-field coupling open a unique opportunity to create strongly absorbing metafilms whose spectral absorption properties directly reflect those of the individual antennas. Using experiments and simulations, we demonstrate that near-unity absorption at one or more target wavelengths of interest can be achieved in a sub-50-nm-thick metafilm using judiciously sized and spaced Ge nanobeams. The ability to create semiconductor metafilms with custom absorption spectra opens up new design strategies for planar optoelectronic devices and solar cells. PMID:26184335

  15. Creating semiconductor metafilms with designer absorption spectra

    PubMed Central

    Kim, Soo Jin; Fan, Pengyu; Kang, Ju-Hyung; Brongersma, Mark L.

    2015-01-01

    The optical properties of semiconductors are typically considered intrinsic and fixed. Here we leverage the rapid developments in the field of optical metamaterials to create ultrathin semiconductor metafilms with designer absorption spectra. We show how such metafilms can be constructed by placing one or more types of high-index semiconductor antennas into a dense array with subwavelength spacings. It is argued that the large absorption cross-section of semiconductor antennas and their weak near-field coupling open a unique opportunity to create strongly absorbing metafilms whose spectral absorption properties directly reflect those of the individual antennas. Using experiments and simulations, we demonstrate that near-unity absorption at one or more target wavelengths of interest can be achieved in a sub-50-nm-thick metafilm using judiciously sized and spaced Ge nanobeams. The ability to create semiconductor metafilms with custom absorption spectra opens up new design strategies for planar optoelectronic devices and solar cells. PMID:26184335

  16. Creating semiconductor metafilms with designer absorption spectra

    NASA Astrophysics Data System (ADS)

    Kim, Soo Jin; Fan, Pengyu; Kang, Ju-Hyung; Brongersma, Mark L.

    2015-07-01

    The optical properties of semiconductors are typically considered intrinsic and fixed. Here we leverage the rapid developments in the field of optical metamaterials to create ultrathin semiconductor metafilms with designer absorption spectra. We show how such metafilms can be constructed by placing one or more types of high-index semiconductor antennas into a dense array with subwavelength spacings. It is argued that the large absorption cross-section of semiconductor antennas and their weak near-field coupling open a unique opportunity to create strongly absorbing metafilms whose spectral absorption properties directly reflect those of the individual antennas. Using experiments and simulations, we demonstrate that near-unity absorption at one or more target wavelengths of interest can be achieved in a sub-50-nm-thick metafilm using judiciously sized and spaced Ge nanobeams. The ability to create semiconductor metafilms with custom absorption spectra opens up new design strategies for planar optoelectronic devices and solar cells.

  17. Stability properties of wines by absorption spectra

    NASA Astrophysics Data System (ADS)

    Larena, A.; Vega, J.

    1986-03-01

    The temporal evolution of absorption spectra (370-700 nm) of different spanish wines has been studied by us under the influence of air presence, and the light exposition. In particular, we have exposed the wines to a magenta light. Nevertheless, the color coordinates of wine show a little relative variation (0.1-1 %)

  18. Absorption Features in Soil Spectra Assessment.

    PubMed

    Vašát, Radim; Kodešová, Radka; Borůvka, Luboš; Jakšík, Ondřej; Klement, Aleš; Drábek, Ondřej

    2015-12-01

    From a wide range of techniques appropriate to relate spectra measurements with soil properties, partial least squares (PLS) regression and support vector machines (SVM) are most commonly used. This is due to their predictive power and the availability of software tools. Both represent exclusively statistically based approaches and, as such, benefit from multiple responses of soil material in the spectrum. However, physical-based approaches that focus only on a single spectral feature, such as simple linear regression using selected continuum-removed spectra values as a predictor variable, often provide accurate estimates. Furthermore, if this approach extends to multiple cases by taking into account three basic absorption feature parameters (area, width, and depth) of all occurring features as predictors and subjecting them to best subset selection, one can achieve even higher prediction accuracy compared with PLS regression. Here, we attempt to further extend this approach by adding two additional absorption feature parameters (left and right side area), as they can be important diagnostic markers, too. As a result, we achieved higher prediction accuracy compared with PLS regression and SVM for exchangeable soil pH, slightly higher or comparable for dithionite-citrate and ammonium oxalate extractable Fe and Mn forms, but slightly worse for oxidizable carbon content. Therefore, we suggest incorporating the multiple linear regression approach based on absorption feature parameters into existing working practices. PMID:26555184

  19. Absorption Features in Soil Spectra Assessment.

    PubMed

    Vašát, Radim; Kodešová, Radka; Borůvka, Luboš; Jakšík, Ondřej; Klement, Aleš; Drábek, Ondřej

    2015-12-01

    From a wide range of techniques appropriate to relate spectra measurements with soil properties, partial least squares (PLS) regression and support vector machines (SVM) are most commonly used. This is due to their predictive power and the availability of software tools. Both represent exclusively statistically based approaches and, as such, benefit from multiple responses of soil material in the spectrum. However, physical-based approaches that focus only on a single spectral feature, such as simple linear regression using selected continuum-removed spectra values as a predictor variable, often provide accurate estimates. Furthermore, if this approach extends to multiple cases by taking into account three basic absorption feature parameters (area, width, and depth) of all occurring features as predictors and subjecting them to best subset selection, one can achieve even higher prediction accuracy compared with PLS regression. Here, we attempt to further extend this approach by adding two additional absorption feature parameters (left and right side area), as they can be important diagnostic markers, too. As a result, we achieved higher prediction accuracy compared with PLS regression and SVM for exchangeable soil pH, slightly higher or comparable for dithionite-citrate and ammonium oxalate extractable Fe and Mn forms, but slightly worse for oxidizable carbon content. Therefore, we suggest incorporating the multiple linear regression approach based on absorption feature parameters into existing working practices.

  20. A new highly selective, ratiometric and colorimetric fluorescence sensor for Cu(2+) with a remarkable red shift in absorption and emission spectra based on internal charge transfer.

    PubMed

    Goswami, Shyamaprosad; Sen, Debabrata; Das, Nirmal Kumar

    2010-02-19

    A new 1,8-diaminonaphthalene based ratiometric and highly selective colorimetric "off-on" type of fluorescent probe, receptor 2 has been designed and synthesized that senses only Cu(2+) among the other heavy and transition metal ions examined on the basis of internal charge transfer (ICT). The visual sensitivity of the receptor 2 is remarkable, showing dual color changes from colorless (receptor) to purple followed by blue and a large red shift in emission upon Cu(2+) complexation.

  1. Optical absorption spectra of dications of carotenoids

    SciTech Connect

    Jeevarajan, J.A.; Wei, C.C.; Jeevarajan, A.S.; Kispert, L.D.

    1996-04-04

    Quantitative optical absorption spectra of the cation radicals and the dications of canthaxanthin (I), {beta}carotene (II), 7`-cyano-7`-ethoxycarbonyl-7`-apo-{beta}-carotene (III), and 7`,7`-dimethyl-7`-apo-{beta}-carotene (IV) in dichloromethane solution are reported. Exclusive formation of dications occurs when the carotenoids are oxidized with ferric chloride. Addition of neutral carotenoid to the dications results in equilibrium formation of cation radicals. Oxidation with iodine in dichloromethane affords only cation radicals; electrochemical oxidation under suitable conditions yields both dications and cation radicals. Values of the optical parameters depend on the nature of the oxidative medium. The oscillator strengths calculated for gas phase cation radicals and dications of I-IV using the INDO/S method show the same trend as the experimental values. 31 refs., 4 figs., 2 tabs.

  2. Determination of individual proton affinities of ofloxacin from its UV-Vis absorption, fluorescence and charge-transfer spectra: effect of inclusion in beta-cyclodextrin on the proton affinities.

    PubMed

    Ghosh, Bankim Chandra; Deb, Nipamanjari; Mukherjee, Asok K

    2010-08-01

    Individual proton affinities of the four dissociable functional groups of (+/-)-9-fluoro-2,3-dihydro-3-methyl-10-(4-methyl-1-piperazinyl)-7-oxo-7H-pyrido[1,2,3-de]-1,4-benzoxazine-6-carboxylic acid (commonly called "ofloxacin" and to be denoted henceforth as OflH), have been determined from the pH-dependent variation of the UV-vis absorption and fluorescence spectra of the compound itself and of its charge transfer complexes (CT) with p-bromanil and p-chloranil (in aqueous medium containing 0.1% ethanol, v/v). To utilize the CT spectra for determination of the proton affinity of the anilinic N, the CT absorption band of the ofloxacin-p-bromanil complex has been studied by changing the pH of the medium. Further, the effect of inclusion on the proton affinities of the four dissociable groups of OflH has been studied in presence of beta-cyclodextrin (beta-CD). Two pK(a) values corresponding to anilinic and tertiary N atoms change, whereas those corresponding to phenolic -OH and aromatic -COOH groups remain unchanged by the addition of beta-CD, a fact that indicates partial inclusion of the ofloxacin molecule in beta-CD. Formation constant and related thermodynamic parameters for the OflH(2)(+).beta-CD inclusion complex in aqueous solution have been determined from absorption intensities. A general relation between pK(a) values of guests having proton-releasing functional groups and formation constants of the inclusion complexes of the protonated and deprotonated forms with a host molecule has been utilized for determination of the formation constant of the OflH(3)(+2).beta-CD complex from the pK(a) values of OflH(3)(+2) in the presence and absence of beta-CD, along with the formation constant of the OflH(2)(+).beta-CD complex. Results of the present study reveal that the N-methylpiperazinyl moiety of ofloxacin is included in beta-CD, and the remaining part of the guest molecule remains outside. Also, in molecular interaction with quinone-type electron acceptors

  3. DNA-Dye-Conjugates: Conformations and Spectra of Fluorescence Probes

    PubMed Central

    Beierlein, Frank R.; Paradas Palomo, Miguel; Sharapa, Dmitry I.; Zozulia, Oleksii; Mokhir, Andriy; Clark, Timothy

    2016-01-01

    Extensive molecular-dynamics (MD) simulations have been used to investigate DNA-dye and DNA-photosensitizer conjugates, which act as reactants in templated reactions leading to the generation of fluorescent products in the presence of specific desoxyribonucleic acid sequences (targets). Such reactions are potentially suitable for detecting target nucleic acids in live cells by fluorescence microscopy or flow cytometry. The simulations show how the attached dyes/photosensitizers influence DNA structure and reveal the relative orientations of the chromophores with respect to each other. Our results will help to optimize the reactants for the templated reactions, especially length and structure of the spacers used to link reporter dyes or photosensitizers to the oligonucleotides responsible for target recognition. Furthermore, we demonstrate that the structural ensembles obtained from the simulations can be used to calculate steady-state UV-vis absorption and emission spectra. We also show how important quantities describing the quenching of the reporter dye via fluorescence resonance energy transfer (FRET) can be calculated from the simulation data, and we compare these for different relative chromophore geometries. PMID:27467071

  4. DNA-Dye-Conjugates: Conformations and Spectra of Fluorescence Probes.

    PubMed

    Beierlein, Frank R; Paradas Palomo, Miguel; Sharapa, Dmitry I; Zozulia, Oleksii; Mokhir, Andriy; Clark, Timothy

    2016-01-01

    Extensive molecular-dynamics (MD) simulations have been used to investigate DNA-dye and DNA-photosensitizer conjugates, which act as reactants in templated reactions leading to the generation of fluorescent products in the presence of specific desoxyribonucleic acid sequences (targets). Such reactions are potentially suitable for detecting target nucleic acids in live cells by fluorescence microscopy or flow cytometry. The simulations show how the attached dyes/photosensitizers influence DNA structure and reveal the relative orientations of the chromophores with respect to each other. Our results will help to optimize the reactants for the templated reactions, especially length and structure of the spacers used to link reporter dyes or photosensitizers to the oligonucleotides responsible for target recognition. Furthermore, we demonstrate that the structural ensembles obtained from the simulations can be used to calculate steady-state UV-vis absorption and emission spectra. We also show how important quantities describing the quenching of the reporter dye via fluorescence resonance energy transfer (FRET) can be calculated from the simulation data, and we compare these for different relative chromophore geometries. PMID:27467071

  5. Absorption and fluorescent spectral studies of imidazophenazine derivatives.

    PubMed

    Ryazanova, O A; Zozulya, V N; Voloshin, I M; Karachevtsev, V A; Makitruk, V L; Stepanian, S G

    2004-07-01

    Absorption and fluorescent spectra as well as fluorescence polarization degree of imidazo-[4,5-d]-phenazine (F1) and its two modified derivatives, 2-trifluoridemethylimidazo-[4,5-d]-phenazine (F2) and 1,2,3-triazole-[4,5-d]-phenazine (F3), were investigated in organic solvents of various polarities and hydrogen bonding abilities. Extinction coefficients of F2 and F3 are increased, their fluorescence Stokes shifts are reduced in comparison with those for unmodified imidazophenazine. For F3 a red shift of the longwave absorption band is observed by 15-20 nm. Modifications of imidazophenazine have led to a sufficient increase of fluorescence polarization degrees that enables to use F2 and F3 as promising fluorescent probes with polarization method application. The configuration, atomic charge distribution and dipole moments of the isolated dye molecules in the ground state were calculated by the DFT method. The computation has revealed that ground state dipole moments of F1, F2, and F3 differ slightly and are equal to 3.5, 3.2, and 3.7D, respectively. The changes in dipole moments upon the optical excitation for all derivatives estimated using Lippert equation were found to be Deltamu = 9 D. The energies of the electronic S1<--S0 transition in solvents of different proton donor abilities were determined, and energetic diagram illustrating the substituent effect was plotted. For nucleoside analogs of these compounds, covalently incorporated into a nucleotide chain, we have considered a possibility to use them as fluorescent reporters of hybridization of antisense oligonucleotides, as well as molecular anchors for its stabilization. PMID:15248979

  6. Optical absorption spectra of pairs of small metal particles

    NASA Astrophysics Data System (ADS)

    Quinten, M.; Kreibig, U.; Schönauer, D.; Genzel, L.

    1985-06-01

    The influence of plasma resonance coupling in small Au particle pairs on their optical properties was calculated including retardation effects. The latter prove to be important for sizes above 15 nm. For pairs of smaller particles a Maxwell-Garnett formula is derived and absorption spectra are calculated explicitly. Comparison with optical absorption spectra measured on aggregated Au particle hydrosols, gives good agreement concerning the splitting up of the dipolar single-particle plasma resonance band.

  7. Absorption and fluorescence properties of fluorescein

    NASA Astrophysics Data System (ADS)

    Sjöback, Robert; Nygren, Jan; Kubista, Mikael

    1995-06-01

    We have characterized the protolytic equilibria of fluorescein and determined the spectroscopic properties of its protolytic forms. The protolytic constants relating the chemical activities (which at low ionic strength equal concentrations) of the cation, neutral form, anion and dianion are p K1 = 2.08, p K2 = 4.31, and p K3 = 6.43. All forms have rather high molar absorptivities being ɛ437FH 3 1 = 53 000, ɛ434FH 2 = 11 000, ɛ453FH- = 29 000 ( ɛ472FH = 29 000) and ɛ490F 2 = 76 900 M -1 cm -1 for the cation, neutral form, anion and dianion, respectively. The dianion has the most intense fluorescence with a quantum yield of 0.93 but also the anion shows considerable fluorescence with a quantum yield of 0.37. The neutral and cationic species are upon excitation converted into the anion and fluoresce with quantum yields of about 0.30 and 0.18, respectively.

  8. An investigation of a mathematical model for atmospheric absorption spectra

    NASA Technical Reports Server (NTRS)

    Niple, E. R.

    1979-01-01

    A computer program that calculates absorption spectra for slant paths through the atmosphere is described. The program uses an efficient convolution technique (Romberg integration) to simulate instrument resolution effects. A brief information analysis is performed on a set of calculated spectra to illustrate how such techniques may be used to explore the quality of the information in a spectrum.

  9. Excitation-emission spectra and fluorescence quantum yields for fresh and aged biogenic secondary organic aerosols

    SciTech Connect

    Lee, Hyun Ji; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey A.

    2013-05-10

    Certain biogenic secondary organic aerosols (SOA) become absorbent and fluorescent when exposed to reduced nitrogen compounds such as ammonia, amines and their salts. Fluorescent SOA may potentially be mistaken for biological particles by detection methods relying on fluorescence. This work quantifies the spectral distribution and effective quantum yields of fluorescence of SOA generated from two monoterpenes, limonene and a-pinene, and two different oxidants, ozone (O3) and hydroxyl radical (OH). The SOA was generated in a smog chamber, collected on substrates, and aged by exposure to ~100 ppb ammonia vapor in air saturated with water vapor. Absorption and excitation-emission matrix (EEM) spectra of aqueous extracts of aged and control SOA samples were measured, and the effective absorption coefficients and fluorescence quantum yields (~0.005 for 349 nm excitation) were determined from the data. The strongest fluorescence for the limonene-derived SOA was observed for excitation = 420+- 50 nm and emission = 475 +- 38 nm. The window of the strongest fluorescence shifted to excitation = 320 +- 25 nm and emission = 425 +- 38 nm for the a-pinene-derived SOA. Both regions overlap with the excitation-emission matrix (EEM) spectra of some of the fluorophores found in primary biological aerosols. Our study suggests that, despite the low quantum yield, the aged SOA particles should have sufficient fluorescence intensities to interfere with the fluorescence detection of common bioaerosols.

  10. Excitation-emission spectra and fluorescence quantum yields for fresh and aged biogenic secondary organic aerosols.

    PubMed

    Lee, Hyun Ji Julie; Laskin, Alexander; Laskin, Julia; Nizkorodov, Sergey A

    2013-06-01

    Certain biogenic secondary organic aerosols (SOA) become absorbent and fluorescent when exposed to reduced nitrogen compounds such as ammonia, amines, and their salts. Fluorescent SOA may potentially be mistaken for biological particles by detection methods relying on fluorescence. This work quantifies the spectral distribution and effective quantum yields of fluorescence of water-soluble SOA generated from two monoterpenes, limonene and α-pinene, and two different oxidants, ozone (O3) and hydroxyl radical (OH). The SOA was generated in a smog chamber, collected on substrates, and aged by exposure to ∼100 ppb ammonia in air saturated with water vapor. Absorption and excitation-emission matrix (EEM) spectra of aqueous extracts of aged and control SOA samples were measured, and the effective absorption coefficients and fluorescence quantum yields (∼0.005 for 349 nm excitation) were determined from the data. The strongest fluorescence for the limonene-derived SOA was observed for λexcitation = 420 ± 50 nm and λemission = 475 ± 38 nm. The window of the strongest fluorescence shifted to λexcitation = 320 ± 25 nm and λemission = 425 ± 38 nm for the α-pinene-derived SOA. Both regions overlap with the EEM spectra of some of the fluorophores found in primary biological aerosols. Despite the low quantum yield, the aged SOA particles may have sufficient fluorescence intensities to interfere with the fluorescence detection of common bioaerosols.

  11. Terahertz absorption spectra and potential energy distribution of liquid crystals.

    PubMed

    Chen, Zezhang; Jiang, Yurong; Jiang, Lulu; Ma, Heng

    2016-01-15

    In this work, the terahertz (THz) absorption spectra of a set of nematic liquid crystals were studied using the density functional theories (DFT). An accurate assignment of the vibrational modes corresponding to absorption frequencies were performed using potential energy distribution (PED) in a frequency range of 0-3 THz. The impacts of different core structures on THz absorption spectra were discussed. The results indicate that scope of application must be considered in the LC-based THz device designing. This proposed work may give a useful suggestion on the design of novel liquid crystal material in THz wave. PMID:26476072

  12. Intrinsic fluorescence spectroscopy in turbid media: disentangling effects of scattering and absorption.

    PubMed

    Müller, M G; Georgakoudi, I; Zhang, Q; Wu, J; Feld, M S

    2001-09-01

    The fluorescence from a turbid medium such as biologic tissue contains information about scattering and absorption, as well as the intrinsic fluorescence, i.e., the fluorescence from an optically thin sample of pure fluorophores. The interplay of scattering and absorption can result in severe distortion of the intrinsic spectral features. These distortions can be removed by use of a photon-migration-based picture and information from simultaneously acquired fluorescence and reflectance spectra. We present experimental evidence demonstrating the validity of such an approach for extracting the intrinsic fluorescence for a wide range of scatterer and absorber concentrations in tissue models, ex vivo and in vivo tissues. We show that variations in line shape and intensity in intrinsic tissue fluorescence are significantly reduced compared with the corresponding measured fluorescence.

  13. Fluorescence Emission and Excitation Spectra of Photo-Fragmented Nitrobenzene.

    NASA Astrophysics Data System (ADS)

    Lue, Christopher J.; Tanjaroon, Chakree; Johnson, J. Bruce; Allen, Susan D.; Reeve, Scott W.

    2012-06-01

    Upon absorption of a UV photon, nitrobenzene readily dissociates into C_6H_5, NO_2, C_6H_5NO, O, C_6H_5O, and NO through three different channels. We have recorded high resolution emission and excitation spectra of the NO resulting from photo-fragmented nitrobenzene using a pulsed picosecond tunable laser and a nanosecond dye laser. Specifically, the lasers probed the A^2Σ^+→ X^2π(1/2,3/2) NO band system between 225-260 nm using an one or two color process. In a one color process, the same energy (wavelength) photon is used to dissociate nitrobenzene and excite NO. In a two color process, photons of a particular energy are used to dissociate the nitrobenzene while photons of a different energy are used to probe the resultant NO. We have determined the rotational and vibrational temperatures of the nascent NO. And, we have examined the effect of the relative timing of the two photons on the fluorescence spectra to extract information about the photodissociation dynamics. Lin, M.-F.; Lee, Y. T.; Ni, C.-K.; Xu, S. and Lin, M. C. J. Chem. Phys., AIP, 2007, 126.

  14. Predicting fluorescence lifetimes and spectra of biopolymers.

    PubMed

    Callis, Patrik R

    2011-01-01

    Use of fluorescence in biology and biochemistry for imaging and characterizing equilibrium and dynamic processes is growing exponentially. Much progress has been made in the last few years on the microscopic understanding of the underlying principles of what controls the wavelength and quenching of fluorescence in biopolymers, both of which are central to the utility of fluorescent probes. This chapter is concerned with the quantitative microscopic understanding and prediction of the fluorescence wavelength and/or intensity of a fluorescent probe molecule attached to a biopolymer as revealed by hybrid quantum and classical mechanical computation procedures. The aim is not only to provide a recipe, but also even more importantly, to communicate the qualitative basic concepts of interpretation of fluorescence. These are surprisingly simple, although not broadly appreciated at this time. In addition, an effort has been made to show how these techniques have led to an emerging understanding of the relation between time-dependent wavelengths shifts due to solvent relaxation and population decay of conformational sub-ensembles.

  15. Identification of THz absorption spectra of chemicals using neural networks

    NASA Astrophysics Data System (ADS)

    Shen, Jingling; Jia, Yan; Liang, Meiyan; Chen, Sijia

    2007-09-01

    Absorption spectra in the range from 0.2 to 2.6 THz of chemicals such as illicit drugs and antibiotics obtaining from Terahertz time-domain spectroscopy technique were identified successfully by artificial neural networks. Back Propagation (BP) and Self-Organizing Feature Map (SOM) were investigated to do the identification or classification, respectively. Three-layer BP neural networks were employed to identify absorption spectra of nine illicit drugs and six antibiotics. The spectra of the chemicals were used to train a BP neural network and then the absorption spectra measured in different times were identified by the trained BP neural network. The average identification rate of 76% was achieved. SOM neural networks, another important neural network which sorts input vectors by their similarity, was used to sort 60 absorption spectra from 6 illicit drugs. The whole network was trained by setting a 20×20 and a 16×16 grid, and both of them had given satisfied clustering results. These results indicate that it is feasible to apply BP and SOM neural networks model in the field of THz spectra identification.

  16. Demonstrating Absorption Spectra Using Commercially Available Incandescent Light Bulbs

    NASA Astrophysics Data System (ADS)

    Birriel, Jennifer J.

    In introductory astronomy courses, I typically introduce the three types of spectra: continuous, absorption line, and emission line. It is standard practice to use an ordinary incandescent light bulb to demonstrate the production of a continuous spectrum, and gas discharge tubes to demonstrate the production of an emission line spectrum. The concept of an absorption spectrum is more difficult for students to grasp. A variety of commercially available light bulbs can be used to demonstrate absorption spectra. Here I discuss the use of specialty incandescent light bulbs to demonstrate the phenomenon of absorption of the continuous spectrum produced by a hot tungsten filament. The bulbs examined include the GE Reveal bulb, yellow anti-insect lights, colored party bulbs, and an incandescent "black light" bulb. The bulbs can be used in a lecture or laboratory setting.

  17. Experimental recovery of intrinsic fluorescence and fluorophore concentration in the presence of hemoglobin: spectral effect of scattering and absorption on fluorescence

    NASA Astrophysics Data System (ADS)

    Du Le, Vinh Nguyen; Patterson, Michael S.; Farrell, Thomas J.; Hayward, Joseph E.; Fang, Qiyin

    2015-12-01

    The ability to recover the intrinsic fluorescence of biological fluorophores is crucial to accurately identify the fluorophores and quantify their concentrations in the media. Although some studies have successfully retrieved the fluorescence spectral shape of known fluorophores, the techniques usually came with heavy computation costs and did not apply for strongly absorptive media, and the intrinsic fluorescence intensity and fluorophore concentration were not recovered. In this communication, an experimental approach was presented to recover intrinsic fluorescence and concentration of fluorescein in the presence of hemoglobin (Hb). The results indicated that the method was efficient in recovering the intrinsic fluorescence peak and fluorophore concentration with an error of 3% and 10%, respectively. The results also suggested that chromophores with irregular absorption spectra (e.g., Hb) have more profound effects on fluorescence spectral shape than chromophores with monotonic absorption and scattering spectra (e.g., black India ink and polystyrene microspheres).

  18. [Transient UV absorption spectra of artemisinin reacting with sodium hydroxide].

    PubMed

    Gao, Yan-Jun; Ping, Li; Yang, Li-Jun; Wang, Qi-Ming; Xue, Jun-Peng; Wu, Da-Cheng; Li, Rui-Xia

    2009-03-01

    UV absorption spectrum of artemisinin and transient absorption spectra of various concentrations of artemisinin reacting with sodium hydroxide were measured by using an intensified spectroscopic detector ICCD. The exposure time of each spectrum was 0.1 ms. Results indicate that artemisinin has an obvious UV absorption band centered at 212.52 nm and can react with sodium hydroxide easily. All absorption spectra of different concentrations of artemisinin reacting with sodium hydroxide have the similar changes, but the moment at which the changes happened is different. After adding sodium hydroxide into artemisinin in ethanol solution, there was a new absorption band centered at 288 nm appearing firstly. As reaction went on, the intensity of another absorption band centered at 260 nm increased gradually. At the end of the reaction, a continuous absorption band from 200 to 350 nm with the peak at 245 nm formed finally. No other transient absorption spectral data are available on the reaction of artemisinin with sodium hydroxide currently. The new spectral information obtained in this experiment provides very important experimental basis for understanding the properties of artemisinin reacting with alkaline medium and is useful for correctly using of artemisinin as a potential anticancer drug.

  19. IR absorption spectra of cellulose obtained from ozonated wood

    NASA Astrophysics Data System (ADS)

    Mamleeva, N. A.; Autlov, S. A.; Kharlanov, A. N.; Bazarnova, N. G.; Lunin, V. V.

    2015-08-01

    The kinetic curves of ozone absorption by aspen wood were obtained. Processing of wood with peracetic acid gave cellulose samples. The yields of ozonated wood, water-soluble compounds, and cellulose were determined for the samples corresponding to different consumptions of ozone. The IR absorption spectra of wood and cellulose isolated from ozonated wood were analyzed. The supramolecular structure of cellulose can be changed by varying the conditions of wood ozonation.

  20. Emission and absorption spectra of some bridged 1,5-benzodiazepines

    NASA Astrophysics Data System (ADS)

    Mellor, J. M.; Pathirana, R. N.; Stibbard, J. H. A.

    Absorption spectra in neutral and acidic media are reported for a series of bridged 1,5-benzodiazepines, which are unable to tautomerize. Comparison is made with non-bridged 1,5-benzodiazepines capable of tautomeric rearrangement. Both bridged and non-bridged 1,5-benzodiazepines are essentially non-fluorescent due to the "proximity effect" of interaction between singlet ηπ* and ππ* states of similar energy, a phenomenon previously recognised in six-membered nitrogen heterocycles.

  1. A method for normalization of X-ray absorption spectra

    SciTech Connect

    Weng, T.-C.; Waldo, G.S.; Penner-Hahn, J.E.

    2010-07-20

    Accurate normalization of X-ray absorption data is essential for quantitative analysis of near-edge features. A method, implemented as the program MBACK, to normalize X-ray absorption data to tabulated mass absorption coefficients is described. Comparison of conventional normalization methods with MBACK demonstrates that the new normalization method is not sensitive to the shape of the background function, thus allowing accurate comparison of data collected in transmission mode with data collected using fluorescence ion chambers or solid-state fluorescence detectors. The new method is shown to have better reliability and consistency and smaller errors than conventional normalization methods. The sensitivity of the new normalization method is illustrated by analysis of data collected during an equilibrium titration.

  2. A Simple Demonstration of Absorption Spectra Using Tungsten Holiday Lights

    ERIC Educational Resources Information Center

    Birriel, Jennifer J.

    2009-01-01

    In a previous paper submitted to the Demonstrations section (Birriel 2008, "Astronomy Education Review," 7, 147), I discussed using commercially available incandescent light bulbs for the purpose of demonstrating absorption spectra in the classroom or laboratory. This demonstration solved a long-standing problem that many of astronomy instructors…

  3. Investigation of formalin influence over hard and soft biological tissues fluorescent spectra in vitro

    NASA Astrophysics Data System (ADS)

    Borisova, E.; Uzunov, Tz.; Vladimirov, B.; Avramov, L.

    2007-05-01

    In order to investigate the formalin influence over fluorescence properties of hard and soft biological tissues during conservation, emission spectra have been registered. Nitrogen laser at 337 nm and light-emitting diode with maximum at 405 nm have been used as excitation sources. For investigation of formalin influence over hard tissues, an experiment was made on teeth samples. Sound teeth were demineralized with a phosphoric acid for 10 seconds to obtain enamel structure near to the tooth lesion, and were fixed in formalin. Before and after teeth treatment spectra from the areas of interest were detected. There were not observed changes in the shape of the teeth spectra, related to the introduction of formalin fluorescence. Samples from mucosa of esophagus and stomach, where initially an ALA/Protoporphyrin IX diagnosis was applied, were used as soft tissue specimens. After fluorescent diagnosis in vivo biopsy samples were obtained from normal and cancerous areas and were conserved in formalin. Initially, spectrum observed has one autofluorescence maximum from the mucous tissue at 500-600 nm and secondary maxima from the protoporphyrin fluorescence at 635 nm and 720 nm, as well as pronounced minima at 540 and 575 nm related to hemoglobin absorption. After formalin conservation hemoglobin absorption was strongly reduced that increases mucous emission signal in green-yellow spectral region. Simultaneously the maxima at 635 nm and 720 nm were reduced. As conclusion we could say that formalin has negligible influence over fluorescence spectra of conserved hard tissues and has more pronounced influence over fluorescence spectra obtained in the case of soft tissue conservation, which has to be taking into account in measurements in vitro.

  4. Discrimination of phytoplankton classes using characteristic spectra of 3D fluorescence spectra

    NASA Astrophysics Data System (ADS)

    Zhang, Qian-Qian; Lei, Shu-He; Wang, Xiu-Lin; Wang, Lei; Zhu, Chen-Jian

    2006-02-01

    The discrimination of phytoplankton classes using the characteristic fluorescence spectra extracted from three-dimensional fluorescence spectra was investigated. Single species cultures of 11 phytoplankton species, representing 5 major phytoplankton divisions, were used. The 3D fluorescence spectra of the cultures grown at different temperatures (20 and 15 °C) and illumination intensities (140, 80 and 30 μM m -2 s -1) were measured and their feature extraction methods were explored. Ordering Rayleigh and Raman scattering data as zero, the obtained excitation-emission matrices were processed by both singular value decomposition (SVD) and trilinear decomposition methods. The resulting first principal component can be regarded as the characteristic spectrum of the original 3D fluorescence spectrum. The analysis shows that such characteristic spectra have a discriminatory capability. At different temperatures, the characteristic spectra of Isochrysis galbana, Platymonas helgolanidica and Skeletonema costatuma have high degrees of similarity to their own species samples, while the spectra similarities of Alexandrium tamarense, Prorocentrum dentatum, Pseudo-nitzschia pungens, Chaetoceros curvisetus, Ch. Debilis, Ch. Didymus and Synechococcus sp. are not as significant as the other three species. C. curvisetus, Ch. Debilis and Ch. Didymus, belonging to genus Chaetoceros, have identical spectra and cannot be discriminated at all. Regarding all six diatom species as one class, the average discriminant error rate is below 9%. It is worth mentioning that the diatom class can be distinguished from A. tamarense and P. dentatum, which belong to Dinophyta.

  5. [Study on three-dimensional fluorescence spectra of Yanghe classical distilled spirits].

    PubMed

    Gu, En-dong; Shi, Ai-min; Zhu, Tuo; Xu, Yan; Chen, Guo-qing

    2008-12-01

    In the present paper, the liquors of Hai zhi lan, Tian zhi lan and Meng zhi lan were selected as the objects, and by using equipment of UV-240 ultra-violet spectrophotometer and Sp-2558 multifunctional spectrometer, their absorption and three-dimensional fluorescence spectra induced by UV light were studied respectively. The maximum absorption wavelengths for all of them were located at 212 and 275 nm, but each has different intensity at 212 nm. Moreover, their three-dimensional fluorescence spectra were detected when they were induced by suitable UV-light, The results show that each of the spirits can emit three strong fluorescence lines at 310, 420 and 610 nm respectively when excited by UV-light at 245 nm. Furthermore, we found each of them can emit another two strong fluorescence lines when they absorb the UV-light at 310 and 345 nm. The authors found that they all have five different fluorescence peaks, but each has different intensity. According to the experimental phenomenon, through a careful analysis, it is pointed out that the differences of the five fluorescence peaks basically reflect the aging process and different content of the liquor. The three different brand yanghe classical liquors were identified fast and accurately. The paper also offered a kind of way to determine the quality and brand of white spirit.

  6. Absorption spectra of crystalline limestones experimentally deformed or tectonised

    NASA Astrophysics Data System (ADS)

    Cervelle, B.; ChayéD'Albissin, M.; Gouet, G.; Visocekas, R.

    1982-11-01

    Diffuse-reflectance spectra have been measured for a series of samples of Carrara marble experimentally deformed under different cylindrical stress ( P = 0, 100, 250, 500, 980 bars). The creation of point defects that results has been shown up classically by irradiation with β rays (40 krads), thus producing a typical blue coloration linked with the formation of colour centres. The diffuse-reflectance spectra, measured on powders with a microscope-spectrometer in the visible range (400-800 nm), allow the determination of the absorption spectra by means of the Kubelka-Munk function. These absorption spectra have been measured for each of the deformed samples, as well as for different fractions of a very deformed specimen subsequently heated at temperatures between 100 and 500° C for a fixed time. In the same way, tectonised crystalline limestones, of various origins, were studied without any other treatment than the irradiation with β rays. From this study the following preliminary conclusions have been drawn: (1) The absorption spectrum of an undeformed but merely irradiated specimen of crystalline limestone is practically monotonous, but in the deformed specimens a broad band of absorption appears, having a maximum at 620 nm with several shoulders, the chief of which is at 520 nm. (2) This absorption band shows the existence of colour centres, the density of which can be estimated relatively by means of the chromaticity coordinates x and y of the C.I.E. obtained from the diffuse-reflectance spectra (C.I.E. = Commission Internationale de l'Éclairage). (3) An overgrinding of calcite generates defects that have the same spectra as those produced during the experimental deformation. Consequently, in obtaining the powders of grain size 50-80 μm needed for the diffuse spectrometry, great care must be exercised. (4) For a given confining pressure, the defect density is proportional to the deformation rate. (5) One can calibrate the effect of the annealing of

  7. Effect of pyridine on infrared absorption spectra of copper phthalocyanine.

    PubMed

    Singh, Sukhwinder; Tripathi, S K; Saini, G S S

    2008-02-01

    Infrared absorption spectra of copper phthalocyanine in KBr pellet and pyridine solution in 400-1625 and 2900-3200 cm(-1)regions are reported. In the IR spectra of solid sample, presence of weak bands, which are forbidden according to the selection rules of D4h point group, is explained on the basis of distortion in the copper phthalocyanine molecule caused by the crystal packing effects. Observation of a new band at 1511 cm(-1) and change in intensity of some other bands in pyridine are interpreted on the basis of coordination of the solvent molecule with the central copper ion.

  8. Spectral signatures of fluorescence and light absorption to identify crude oils found in the marine environment

    NASA Astrophysics Data System (ADS)

    Baszanowska, E.; Otremba, Z.

    2014-08-01

    To protect the natural marine ecosystem, it is necessary to continuously enhance knowledge of environmental contamination, including oil pollution. Therefore, to properly track the qualitative and quantitative changes in the natural components of seawater, a description of the essential spectral features describing petroleum products is necessary. This study characterises two optically-different types of crude oils (Petrobaltic and Romashkino) - substances belonging to multi-fluorophoric systems. To obtain the spectral features of crude oils, the excitation-emission spectroscopy technique was applied. The fluorescence and light absorption properties for various concentrations of oils at a stabilised temperature are described. Both excitation-emission spectra (EEMs) and absorption spectra of crude oils are discussed. Based on the EEM spectra, both excitation end emission peaks for the wavelengthindependent fluorescence maximum (Exmax/ Emmax) - characteristic points for each type of oil - were identified and compared with the literature data concerning typical marine chemical structures.

  9. Infrared absorption spectra of metal carbides, nitrides and sulfides

    NASA Technical Reports Server (NTRS)

    Kammori, O.; Sato, K.; Kurosawa, F.

    1981-01-01

    The infrared absorption spectra of 12 kinds of metal carbides, 11 kinds of nitrides, and 7 kinds of sulfides, a total of 30 materials, were measured and the application of the infrared spectra of these materials to analytical chemistry was discussed. The measurements were done in the frequency (wave length) range of (1400 to 400/cm (7 to 25 mu). The carbides Al4C3, B4C, the nitrides AlN, BN, Si3N4, WB, and the sulfides Al2S3, FeS2, MnS, NiS and PbS were noted to have specific absorptions in the measured region. The sensitivity of Boron nitride was especially good and could be detected at 2 to 3 micrograms in 300 mg of potassium bromide.

  10. EPR and electronic absorption spectra of copper bearing turquoise mineral

    NASA Astrophysics Data System (ADS)

    Sharma, K. B. N.; Moorthy, L. R.; Reddy, B. J.; Vedanand, S.

    1988-10-01

    Electron paramagnetic resonance and optical absorption spectra of turquoise have been studied both at room and low temperatures. It is concluded from the EPR spectra that the ground state of Cu 2+ ion in turquoise is 2A g(d x2- y2) and it is sited in an elongated rhombic octahedron (D 2π). The observed absorption bands at 14970 and 18354 cm -1 are assigned at 2A g→ 2B 1 g( dx2- y2→ xy) and 2A g→[ su2B 3g(d x 2-y 2→d yz) respectively assuming D 2π symmetry which are inconsistent with EPR studies. The three bands in the NIR region are attributed to combinations of fundamental modes of the H 2O molecule present in the sample.

  11. Fluorescence contribution to reflectance spectra for a variety of coastal waters

    NASA Astrophysics Data System (ADS)

    Gilerson, A.; Zhou, J.; Hlaing, S.; Ioannou, I.; Amin, R.; Gross, B.; Moshary, F.; Ahmed, S.

    2007-09-01

    Improved remote sensing retrievals of the chlorophyll fluorescence component in coastal water reflectance can significantly help environmental impact assessments. While retrieval of chlorophyll fluorescence from satellite observations of open ocean reflectance using Fluorescence Line Height (FLH) algorithms is now routine, it is much more complicated in coastal waters where the fluorescence overlaps with a NIR elastic scattering peak arising from the combination of photosynthetic pigment and particulate scattering and absorption, and rapidly increasing water absorption. To examine retrieval accuracies attainable in coastal waters by MODIS and other FLH algorithms, we compared the results of extensive numerical simulations with those of our field measurements in the Chesapeake Bay. The relationship between the contribution of fluorescence in the reflectance spectra and [Chl] and other water constituents was analyzed by simulations of more than 1000 reflectances using the HYDROLIGHT radiative transfer program. For these, IOP were related to parameterized microphysical models, following the same procedures used to generate the IOCCG dataset, but with higher (1 nm) spectral resolution, and wider range of parameters including chlorophyll specific absorption more typical of coastal waters. Results of simulations and field measurements show that the variability of retrieved fluorescence can be attributed largely to its attenuation in the water by algae, CDOM and mineral particles, and much less to the variation of the fluorescence quantum yield. Our systematic parametric study of fluorescence as a function of the other water components is then used to define the range of water parameters where fluorescence contributes significantly to the NIR peak reflectance, and where it is almost undetectable.

  12. Optical absorption spectra of palladium doped gold cluster cations

    SciTech Connect

    Kaydashev, Vladimir E.; Janssens, Ewald Lievens, Peter

    2015-01-21

    Photoabsorption spectra of gas phase Au{sub n}{sup +} and Au{sub n−1}Pd{sup +} (13 ≤ n ≤ 20) clusters were measured using mass spectrometric recording of wavelength dependent Xe messenger atom photodetachment in the 1.9–3.4 eV photon energy range. Pure cationic gold clusters consisting of 15, 17, and 20 atoms have a higher integrated optical absorption cross section than the neighboring sizes. It is shown that the total optical absorption cross section increases with size and that palladium doping strongly reduces this cross section for all investigated sizes and in particular for n = 14–17 and 20. The largest reduction of optical absorption upon Pd doping is observed for n = 15.

  13. The photophysics of phenylenevinylene oligomers and self-absorption of their fluorescence in polymer films.

    PubMed

    Winch, Nicola M; Smith, Gerald J; Breukers, Robert D; Bhuiyan, Delower H; Kay, Andrew J; Smith, Trevor A; Ghiggino, Kenneth P; Raymond, Sebastiampillai G

    The fluorescence spectra, quantum yields and lifetimes of a series of alkoxy-substituted phenylenevinylene molecules, which serve as short chain oligomer models for poly(p-phenylenevinylene), have been determined in fluid solvents and in a high viscosity polymer matrix. The effects of solvent polarity and a high viscosity molecular environment on the fluorescence yields and spectral shapes have been established. Alkoxy group substitution on the phenyl ring moieties of the molecules has an important effect on the vibronic structures and profiles of the absorption spectra. This was interpreted in terms of hot-band, ground to excited singlet state transitions from energetically closely-spaced torsional vibrational levels of the vinylene double bond in the ground state. The shapes of the absorption bands affect the overlaps of the absorption and fluorescence spectra. This has been quantified as the probability of fluorescence reabsorption in solid polymer films as a function of pathlength. This is an important determinant of the efficacies of these compounds for "harvesting" solar energy in luminescent solar concentrator systems. The reabsorption probabilities of these compounds are lower for all pathlengths than those determined in the same polymer film for the fluorophores, perylene and perylene diimide, which have been considered for concentrating spatially diffuse sunlight. PMID:27480331

  14. [Study on fluorescence spectra of Chinese rice wine].

    PubMed

    Liu, Zhou-yi; Zhu, Tuo; Gu, En-dong; Liu, Ying; Song, Chun-yuan

    2008-10-01

    Chinese rice wine has a history of more than 5000 years, only in China, hich is called "Nation Wine", and Shao Xing Chinese rice wine is a representative of it. The fluorescence spectra of 3 kinds of Shao Xing Chinese rice wine with different storage age induced by suitable UV-light were obtained in the present paper through experiment. The authors compared and analyzed them comprehensively by using three dimensional contour and two dimensional fluorescence technique, and found that their best induced light was all in the vicinity of 370 nm. The peak wavelength of 3 year storage age wine was 504 nm, while 488 nm and 505 nm were for 5 and 8 year storage age wine respectively. The emitted fluorescence existed in 400 to 680 nm, which had wide peak. More over, the emitting mechanism of Shao Xing Chinese rice wine was discussed. The authors also have explained the similarity and difference of fluorescence spectra among the 3 kinds of wine. The reason for wide fluorescence peak was also analyzed. This investigation contributes to the study of the characteristic, year detection and food safety of Chinese rice wine.

  15. Absorption Features in Spectra of Magnetized Neutron Stars

    SciTech Connect

    Suleimanov, V.; Hambaryan, V.; Neuhaeuser, R.; Potekhin, A. Y.; Pavlov, G. G.; Adelsberg, M. van; Werner, K.

    2011-09-21

    The X-ray spectra of some magnetized isolated neutron stars (NSs) show absorption features with equivalent widths (EWs) of 50-200 eV, whose nature is not yet well known.To explain the prominent absorption features in the soft X-ray spectra of the highly magnetized (B{approx}10{sup 14} G) X-ray dim isolated NSs (XDINSs), we theoretically investigate different NS local surface models, including naked condensed iron surfaces and partially ionized hydrogen model atmospheres, with semi-infinite and thin atmospheres above the condensed surface. We also developed a code for computing light curves and integral emergent spectra of magnetized neutron stars with various temperature and magnetic field distributions over the NS surface. We compare the general properties of the computed and observed light curves and integral spectra for XDINS RBS 1223 and conclude that the observations can be explained by a thin hydrogen atmosphere above the condensed iron surface, while the presence of a strong toroidal magnetic field component on the XDINS surface is unlikely.We suggest that the harmonically spaced absorption features in the soft X-ray spectrum of the central compact object (CCO) 1E 1207.4-5209 (hereafter 1E 1207) correspond to peaks in the energy dependence of the free-free opacity in a quantizing magnetic field, known as quantum oscillations. To explore observable properties of these quantum oscillations, we calculate models of hydrogen NS atmospheres with B{approx}10{sup 10}-10{sup 11} G(i.e., electron cyclotron energy E{sub c,e}{approx}0.1-1 keV) and T{sub eff} = 1-3 MK. Such conditions are thought to be typical for 1E 1207. We show that observable features at the electron cyclotron harmonics with EWs {approx_equal}100-200 eV can arise due to these quantum oscillations.

  16. Nonlinear fitting of absorption edges in K-edge densitometry spectra

    SciTech Connect

    Collins, M.; Hsue, Sin-Tao

    1997-11-01

    A new method for analyzing absorption edges in K-Edge Densitometry (KED) spectra is introduced. This technique features a nonlinear function that specifies the empirical form of a broadened K-absorption edge. Nonlinear fitting of the absorption edge can be used to remove broadening effects from the KED spectrum. This allows more data near the edge to be included in the conventional KED fitting procedure. One possible benefit is enhanced precision of measured uranium and plutonium concentrations. Because no additional hardware is required, several facilities that use KED may eventually benefit from this approach. Applications of nonlinear KED fitting in the development of the Los Alamos National Laboratory (LANL) hybrid K-edge/x-ray fluorescence (XRF) densitometer system are described.

  17. Transient absorption spectra of the laser-dressed hydrogen atom

    NASA Astrophysics Data System (ADS)

    Murakami, Mitsuko; Chu, Shih-I.

    2013-10-01

    We present a theoretical study of transient absorption spectra of laser-dressed hydrogen atoms, based on numerical solutions of the time-dependent Schrödinger equation. The timing of absorption is controlled by the delay between an extreme ultra violet (XUV) pulse and an infrared (IR) laser field. The XUV pulse is isolated and several hundred attoseconds in duration, which acts as a pump to drive the ground-state electron to excited p states. The subsequent interaction with the IR field produces dressed states, which manifest as sidebands between the 1s-np absorption spectra separated by one IR-photon energy. We demonstrate that the population of dressed states is maximized when the timing of the XUV pulse coincides with the zero crossing of the IR field, and that their energies can be manipulated in a subcycle time scale by adding a chirp to the IR field. An alternative perspective to the problem is to think of the XUV pulse as a probe to detect the dynamical ac Stark shifts. Our results indicate that the accidental degeneracy of the hydrogen excited states is removed while they are dressed by the IR field, leading to large ac Stark shifts. Furthermore, we observe the Autler-Townes doublets for the n=2 and 3 levels using the 656 nm dressing field, but their separation does not agree with the prediction by the conventional three-level model that neglects the dynamical ac Stark shifts.

  18. Measurement of Fluorescence Spectra from Ambient Aerosol Particles Using Laser-induced Fluorescence Technique

    NASA Astrophysics Data System (ADS)

    Taketani, F.; Kanaya, Y.; Nakamura, T.; Moteki, N.; Takegawa, N.

    2011-12-01

    To obtain the information of composition of organic aerosol particles in atmosphere, we developed an instrument using laser-induced fluorescence (LIF) technique. To measure the fluorescence from a particle, we employed two lasers. Scattering light signal derived from a single particle upon crossing the 635nm-CW laser triggers the 266nm-pulsed laser to excite the particle. Fluorescence from the particle in the wavelength range 300-600nm is spectrally dispersed by a grating spectrometer and then detected by a 32-Ch photo-multiplier tube(PMT). The aerosol stream is surrounded by a coaxial sheath air flow and delivered to the optical chamber at atmospheric pressure. Using PSL particles with known sizes, we made a calibration curve to estimate particle size from scattering light intensity. With the current setup of the instrument we are able to detect both scattering and fluorescence from particles whose diameters are larger than 0.5um. Our system was able to differentiate particles composed of mono-aromatic species (e.g. Tryptophan) from those of Riboflavin, by their different fluorescence wavelengths. Also, measurements of fluorescence spectra of ambient particles were demonstrated in our campus in Yokosuka city, facing Tokyo bay in Japan. We obtained several types of florescence spectra in the 8 hours. Classification of the measured fluorescence spectra will be discussed in the presentation.

  19. Implantable CMOS imaging device with absorption filters for green fluorescence imaging

    NASA Astrophysics Data System (ADS)

    Sunaga, Yoshinori; Haruta, Makito; Takehara, Hironari; Ohta, Yasumi; Motoyama, Mayumi; Noda, Toshihiko; Sasagawa, Kiyotaka; Tokuda, Takashi; Ohta, Jun

    2014-03-01

    Green fluorescent materials such as Green Fluorescence Protein (GFP) and fluorescein are often used for observing neural activities. Thus, it is important to observe the fluorescence in a freely moving state in order to understand neural activities corresponding to behaviors. In this work, we developed an implantable CMOS imaging device for in-vivo green fluorescence imaging with efficient excitation light rejection using a combination of absorption filters. An interference filter is usually used for a fluorescence microscope in order to achieve high fluorescence imaging sensitivity. However, in the case of the implantable device, interference filters are not suitable because their transmission spectra depend on incident angle. To solve this problem we used two kinds of absorption filters that do not have angle dependence. An absorption filter consisting of yellow dye (VARYFAST YELLOW 3150) was coated on the pixel array of an image sensor. The rejection ratio of ideal excitation light (490 nm) against green fluorescence (510 nm) was 99.66%. However, the blue LED as an excitation light source has a broad emission spectrum and its intensity at 510 nm is 2.2 x 10-2 times the emission peak intensity. By coating LEDs with the emission absorption filters, the intensity of the unwanted component of the excitation light was reduced to 1.4 x 10-4. Using the combination of absorption filters, we achieved excitation light transmittance of 10-5 onto the image sensor. It is expected that high-sensitivity green fluorescence imaging of neural activities in a freely moving mouse will be possible by using this technology.

  20. Effects of compositional variation on absorption spectra of lunar pyroxenes

    NASA Technical Reports Server (NTRS)

    Hazen, R. M.; Bell, P. M.; Mao, H. K.

    1978-01-01

    Polarized absorption spectra of lunar pyroxenes with a range of iron, calcium, magnesium, titanium and chromium contents were measured on polished, oriented single crystals; spectral data on pure synthetic FeSiO3 were also recorded. The bands at 1 and 2 microns were found to vary significantly in position with composition within the pyroxene quadrilateral; wavelengths increased with increasing calcium and iron. In the visible region, a weak band at 640 nm correlates in intensity with Cr2O3, but not with titanium as had been previously suggested. The 505-nm ferrous iron peak is a sharp doublet in most low-calcium pyroxenes but a singlet in augites. A peak at 475 nm and an intense absorption edge below 700 nm correlated with titanium content.

  1. Optical absorption and scattering spectra of pathological stomach tissues

    NASA Astrophysics Data System (ADS)

    Giraev, K. M.; Ashurbekov, N. A.; Lakhina, M. A.

    2011-03-01

    Diffuse reflection spectra of biotissues in vivo and transmission and reflection coefficients for biotissues in vitro are measured over 300-800 nm. These data are used to determine the spectral absorption and scattering indices and the scattering anisotropy factor for stomach mucous membranes under normal and various pathological conditions (chronic atrophic and ulcerous defects, malignant neoplasms). The most importan tphysiological (hemodynamic and oxygenation levels) and structural-morphological (scatterer size and density) parameters are also determined. The results of a morphofunctional study correlate well with the optical properties and are consistent with data from a histomorphological analysis of the corresponding tissues.

  2. Observational Cosmology Using Absorption Lines in Quasar Spectra

    NASA Astrophysics Data System (ADS)

    Aghaee, A.

    2016-09-01

    Distant, highly luminous quasars are important cosmological probes for a variety of astrophysical questions: the first generation of galaxies, the star formation history and metal enrichment in the early Universe, the growth of the first super massive black holes (SMBHs), the role of feedback from quasars and SMBHs in galaxy evolution, the epoch of reionization, etc. In addition, they are used as background illuminating source that reveal any object located by chance on the line of sight. I will present our group works in these issues that can be done using absorption lines in the quasar spectra.

  3. Absorption Reconstruction Improves Biodistribution Assessment of Fluorescent Nanoprobes Using Hybrid Fluorescence-mediated Tomography

    PubMed Central

    Gremse, Felix; Theek, Benjamin; Kunjachan, Sijumon; Lederle, Wiltrud; Pardo, Alessa; Barth, Stefan; Lammers, Twan; Naumann, Uwe; Kiessling, Fabian

    2014-01-01

    Aim: Fluorescence-mediated tomography (FMT) holds potential for accelerating diagnostic and theranostic drug development. However, for proper quantitative fluorescence reconstruction, knowledge on optical scattering and absorption, which are highly heterogeneous in different (mouse) tissues, is required. We here describe methods to assess these parameters using co-registered micro Computed Tomography (µCT) data and nonlinear whole-animal absorption reconstruction, and evaluate their importance for assessment of the biodistribution and target site accumulation of fluorophore-labeled drug delivery systems. Methods: Besides phantoms with varying degrees of absorption, mice bearing A431 tumors were imaged 15 min and 48 h after i.v. injection of a fluorophore-labeled polymeric drug carrier (pHPMA-Dy750) using µCT-FMT. The outer shape of mice and a scattering map were derived using automated segmentation of the µCT data. Furthermore, a 3D absorption map was reconstructed from the trans-illumination data. We determined the absorption of five interactively segmented regions (heart, liver, kidney, muscle, tumor). Since blood is the main near-infrared absorber in vivo, the absorption was also estimated from the relative blood volume (rBV), determined by contrast-enhanced µCT. We compared the reconstructed absorption with the rBV-based values and analyzed the effect of using the absorption map on the fluorescence reconstruction. Results: Phantom experiments demonstrated that absorption reconstruction is possible and necessary for quantitative fluorescence reconstruction. In vivo, the reconstructed absorption showed high values in strongly blood-perfused organs such as the heart, liver and kidney. The absorption values correlated strongly with the rBV-based absorption values, confirming the accuracy of the absorption reconstruction. Usage of homogenous absorption instead of the reconstructed absorption map resulted in reduced values in the heart, liver and kidney, by

  4. Fluorescence spectra of blood and urine for cervical cancer detection

    NASA Astrophysics Data System (ADS)

    Masilamani, Vadivel; AlSalhi, Mohamad Saleh; Vijmasi, Trinka; Govindarajan, Kanaganaj; Rathan Rai, Ram; Atif, Muhammad; Prasad, Saradh; Aldwayyan, Abdullah S.

    2012-09-01

    In the current study, the fluorescence emission spectra (FES) and Stokes shift spectra (SSS) of blood and urine samples of cervical cancer patients were obtained and compared to those of normal controls. Both spectra showed that the relative intensity of biomolecules such as porphyrin, collagen, Nicotinamide adenine dinucleotide, and flavin were quite out of proportion in cervical cancer patients. The biochemical mechanism for the elevation of these fluorophores is not yet definitive; nevertheless, these biomolecules could serve as tumor markers for diagnosis, screening, and follow-up of cervical cancers. To the best of our knowledge, this is the first report on FES and SSS of blood and urine of cervical cancer patients to give a sensitivity of 80% and specificity of 78%.

  5. Laser induced fluorescence spectra of fluorophenol cations in a Ne matrix

    USGS Publications Warehouse

    Bondybey, V.E.; English, J.H.; Miller, T.A.; Shiley, R.H.

    1983-01-01

    Laser induced fluorescence and/or absorption spectra of the cations of 2,3,5,6‐tetrafluorophenol, 2,3,5,6‐tetrafluorothiophenol, and 3,5‐difluorophenol have been obtained in a Ne matrix. The spectra of C6HF4OH+ are much better resolved than in the gas phase. The gas phase congestion is likely caused by the near degeneracy of the and electronic states whose separation is now measured at 207 cm−1. The spectrum of C6H3F2OH+ represents a deperturbed example of the Jahn–Teller distorted sym‐C6F3H3+ ion. C6H3F2SH+ shows only a broad featureless absorption.

  6. Experimental research of fluorescence spectra of watercress stressed by lack or excess of watering

    NASA Astrophysics Data System (ADS)

    Bullo, O. A.; Fedotov, Yu. V.; Belov, M. L.; Gorodnichev, V. A.

    2015-11-01

    Experimental laboratory investigations of the laser-induced fluorescence spectra of watercress were conducted. The fluorescence spectra were excited by a YAG:Nd laser emitting at 532 nm. The laboratory setup was described and fluorescence spectra of watercress in stressed states caused by lack and excess of water were presented. It was established that the influence of stress caused by lack and excess of watering is manifested in changes of fluorescence spectra.

  7. Effect of arsenic on reflectance spectra and chlorophyll fluorescence of aquatic plants.

    PubMed

    Iriel, Analia; Dundas, Gavin; Fernández Cirelli, Alicia; Lagorio, Maria G

    2015-01-01

    Arsenic pollution of groundwater is a serious problem in many regions of Latin America that causes severe risks to human health. As a consequence, non-destructive monitoring methodologies, sensitive to arsenic presence in the environment and able to perform a rapid screening of large polluted areas, are highly sought-after. Both chlorophyll - a fluorescence and reflectance of aquatic plants may be potential indicators to sense toxicity in water media. In this work, the effects of arsenic on the optical and photophysical properties of leaves of different aquatic plants (Vallisneria gigantea, Azolla filiculoides and Lemna minor) were evaluated. Reflectance spectra were recorded for the plant leaves from 300 to 2400 nm. The spectral distribution of the fluorescence was also studied and corrected for light re-absorption processes. Photosynthetic parameters (Fv/Fm and ΦPSII) were additionally calculated from the variable chlorophyll fluorescence recorded with a pulse amplitude modulated fluorometer. Fluorescence and reflectance properties for V. gigantea and A. filiculoides were sensitive to arsenic presence in contrast to the behaviour of L. minor. Observed changes in fluorescence spectra could be interpreted in terms of preferential damage in photosystem II. The quantum efficiency of photosystem II for the first two species was also affected, decreasing upon arsenic treatment. As a result of this research, V. gigantea and A. filiculoides were proposed as bioindicators of arsenic occurrence in aquatic media.

  8. Effect of arsenic on reflectance spectra and chlorophyll fluorescence of aquatic plants.

    PubMed

    Iriel, Analia; Dundas, Gavin; Fernández Cirelli, Alicia; Lagorio, Maria G

    2015-01-01

    Arsenic pollution of groundwater is a serious problem in many regions of Latin America that causes severe risks to human health. As a consequence, non-destructive monitoring methodologies, sensitive to arsenic presence in the environment and able to perform a rapid screening of large polluted areas, are highly sought-after. Both chlorophyll - a fluorescence and reflectance of aquatic plants may be potential indicators to sense toxicity in water media. In this work, the effects of arsenic on the optical and photophysical properties of leaves of different aquatic plants (Vallisneria gigantea, Azolla filiculoides and Lemna minor) were evaluated. Reflectance spectra were recorded for the plant leaves from 300 to 2400 nm. The spectral distribution of the fluorescence was also studied and corrected for light re-absorption processes. Photosynthetic parameters (Fv/Fm and ΦPSII) were additionally calculated from the variable chlorophyll fluorescence recorded with a pulse amplitude modulated fluorometer. Fluorescence and reflectance properties for V. gigantea and A. filiculoides were sensitive to arsenic presence in contrast to the behaviour of L. minor. Observed changes in fluorescence spectra could be interpreted in terms of preferential damage in photosystem II. The quantum efficiency of photosystem II for the first two species was also affected, decreasing upon arsenic treatment. As a result of this research, V. gigantea and A. filiculoides were proposed as bioindicators of arsenic occurrence in aquatic media. PMID:25150973

  9. TDDFT prediction of UV-vis absorption and emission spectra of tocopherols in different media.

    PubMed

    Bakhouche, Kahina; Dhaouadi, Zoubeida; Lahmar, Souad; Hammoutène, Dalila

    2015-06-01

    We use the TDDFT/PBE0/6-31+G* method to determine the electronic absorption and emission energies, in different media, of the four forms of tocopherol, which differ by the number and the position of methyl groups on the chromanol. Geometries of the ground state S0 and the first singlet excited state S1 were optimized in the gas phase, and various solvents. The solvent effect is evaluated using an implicit solvation model (IEF-PCM). Our results are compared to the experimental ones obtained for the vitamin E content in several vegetable oils. For all forms of tocopherols, the HOMO-LUMO first vertical excitation is a π-π* transition. Gas phase and non-polar solvents (benzene and toluene) give higher absorption wavelengths than polar solvents (acetone, ethanol, methanol, DMSO, and water); this can be interpreted by a coplanarity between the O-H group and the chroman, allowing a better electronic resonance of the oxygen lone pairs and the aromatic ring, and therefore giving an important absorption wavelength, whereas the polar solvents give high emission wavelengths comparatively to gas phase and non-polar solvents. Fluorescence spectra permit the determination, the separation, and the identification of the four forms of tocopherols by a large difference in emission wavelength values. Graphical Abstract Scheme from process methodological to obtain the absorption and emission spectra for tocopherols.

  10. Multiphoton cascade absorption in single molecule fluorescence saturation spectroscopy.

    PubMed

    Winckler, Pascale; Jaffiol, Rodolphe

    2013-05-01

    Saturation spectroscopy is a relevant method to investigate photophysical parameters of single fluorescent molecules. Nevertheless, the impact of a gradual increase, over a broad range, of the laser excitation on the intramolecular dynamics is not completely understood, particularly concerning their fluorescence emission (the so-called brightness). Thus, we propose a comprehensive theoretical and experimental study to interpret the unexpected evolution of the brightness with the laser power taking into account the cascade absorption of two and three photons. Furthermore, we highlight the key role played by the confocal observation volume in fluorescence saturation spectroscopy of single molecules in solution.

  11. Real-time absorption reduced surface fluorescence imaging

    PubMed Central

    Yang, Bin; Tunnell, James W.

    2014-01-01

    Abstract. We introduce a technique that limits absorption effects in fluorescence imaging and does not require extensive imaging processing, thus allowing for video rate imaging. The absorption minimization is achieved using spatial frequency domain imaging at a single high spatial frequency with standard three-phase demodulation. At a spatial frequency f=0.5  mm−1, we demonstrated in both in-vitro phantoms and ex-vivo tissue that the absorption can be significantly reduced. In the real-time implementation, we achieved a video rate of 19  frames/s. This technique has potential in cancer visualization and tumor margin detection. PMID:25250826

  12. Real-time absorption reduced surface fluorescence imaging.

    PubMed

    Yang, Bin; Tunnell, James W

    2014-09-01

    We introduce a technique that limits absorption effects in fluorescence imaging and does not require extensive imaging processing, thus allowing for video rate imaging. The absorption minimization is achieved using spatial frequency domain imaging at a single high spatial frequency with standard three-phase demodulation. At a spatial frequency f ¼ 0.5 mm−1, we demonstrated in both in-vitro phantoms and ex-vivo tissue that the absorption can be significantly reduced. In the real-time implementation, we achieved a video rate of 19 frames∕s. This technique has potential in cancer visualization and tumor margin detection. PMID:25250826

  13. Atomic Absorption, Atomic Fluorescence, and Flame Emission Spectrometry.

    ERIC Educational Resources Information Center

    Horlick, Gary

    1984-01-01

    This review is presented in six sections. Sections focus on literature related to: (1) developments in instrumentation, measurement techniques, and procedures; (2) performance studies of flames and electrothermal atomizers; (3) applications of atomic absorption spectrometry; (4) analytical comparisons; (5) atomic fluorescence spectrometry; and (6)…

  14. Absorption spectra of adenocarcinoma and squamous cell carcinoma cervical tissues

    NASA Astrophysics Data System (ADS)

    Ivashko, Pavlo; Peresunko, Olexander; Zelinska, Natalia; Alonova, Marina

    2014-08-01

    We studied a methods of assessment of a connective tissue of cervix in terms of specific volume of fibrous component and an optical density of staining of connective tissue fibers in the stroma of squamous cancer and cervix adenocarcinoma. An absorption spectra of blood plasma of the patients suffering from squamous cancer and cervix adenocarcinoma both before the surgery and in postsurgical periods were obtained. Linear dichroism measurements transmittance in polarized light at different orientations of the polarization plane relative to the direction of the dominant orientation in the structure of the sample of biotissues of stroma of squamous cancer and cervix adenocarcinoma were carried. Results of the investigation of the tumor tissues showed that the magnitude of the linear dichroism Δ is insignificant in the researched spectral range λ=280-840 nm and specific regularities in its change observed short-wave ranges.

  15. Theoretical study on absorption and emission spectra of pyrrolo-C analogues

    NASA Astrophysics Data System (ADS)

    Liu, Hongxia; Liu, Jianhua; Yang, Yan; Li, Yan; Wang, Haijun

    2015-01-01

    Fluorescent nucleoside analogues have attracted much attention in studying the structure and dynamics of nucleic acids in recent years. In the present work, we use theoretical calculations to investigate the structural and optical properties of Pyrrolo-C (PyC) and its analogues which are modified via the conjugation or fusion of different aromatic ring to the PyC core. We also consider the effects of aqueous solution and base pairing. The results show that the fluorescent pyrrolo-C analogues can pair with guanosine to form stable H-bonded WC base pairs. The calculated absorption peaks of modified deoxyribonucleosides agree well with the measured data. The absorption and emission maxima of the pyrrolo-C analogues are greatly red shifted compared with nature C. The solvent effects can induce wavelength blue shift and increase the oscillator strengths in both the absorption and emission spectra. With regard to the WC base pairs, the B3LYP functional reveals that the lowest energy transitions of modified GC base pairs are charge transfer excitation while the CAM-B3LYP functional predicts that all the lowest transitions are localised on the pyrrolo-C analogues. The M062X and CAM-B3LYP functionals show good agreement with respect to both the value of the lowest energy transitions as well as the oscillator strengths.

  16. A Parallel Iterative Method for Computing Molecular Absorption Spectra.

    PubMed

    Koval, Peter; Foerster, Dietrich; Coulaud, Olivier

    2010-09-14

    We describe a fast parallel iterative method for computing molecular absorption spectra within TDDFT linear response and using the LCAO method. We use a local basis of "dominant products" to parametrize the space of orbital products that occur in the LCAO approach. In this basis, the dynamic polarizability is computed iteratively within an appropriate Krylov subspace. The iterative procedure uses a matrix-free GMRES method to determine the (interacting) density response. The resulting code is about 1 order of magnitude faster than our previous full-matrix method. This acceleration makes the speed of our TDDFT code comparable with codes based on Casida's equation. The implementation of our method uses hybrid MPI and OpenMP parallelization in which load balancing and memory access are optimized. To validate our approach and to establish benchmarks, we compute spectra of large molecules on various types of parallel machines. The methods developed here are fairly general, and we believe they will find useful applications in molecular physics/chemistry, even for problems that are beyond TDDFT, such as organic semiconductors, particularly in photovoltaics.

  17. Substitution effects on the absorption spectra of nitrophenolate isomers.

    PubMed

    Wanko, Marius; Houmøller, Jørgen; Støchkel, Kristian; Suhr Kirketerp, Maj-Britt; Petersen, Michael Åxman; Nielsen, Mogens Brøndsted; Nielsen, Steen Brøndsted; Rubio, Angel

    2012-10-01

    Charge-transfer excitations highly depend on the electronic coupling between the donor and acceptor groups. Nitrophenolates are simple examples of charge-transfer systems where the degree of coupling differs between ortho, meta and para isomers. Here we report the absorption spectra of the isolated anions in vacuo to avoid the complications of solvent effects. Gas-phase action spectroscopy was done with two different setups, an electrostatic ion storage ring and an accelerator mass spectrometer. The results are interpreted on the basis of CC2 quantum chemical calculations. We identified absorption maxima at 393, 532, and 399 nm for the para, meta, and ortho isomer, respectively, with the charge-transfer transition into the lowest excited singlet state. In the meta isomer, this π-π* transition is strongly redshifted and its oscillator strength reduced, which is related to the pronounced charge-transfer character, as a consequence of the topology of the conjugated π-system. Each isomer's different charge distribution in the ground state leads to a very different solvent shift, which in acetonitrile is bathochromic for the para and ortho, but hypsochromic for the meta isomer.

  18. Fluorescence spectra of benign and malignant prostate tissues

    NASA Astrophysics Data System (ADS)

    AlSalhi, M. S.; Masilamani, V.; Atif, M.; Farhat, K.; Rabah, D.; Turki, M. R. Al

    2012-09-01

    In this study, fluorescence emission spectrum (FES), Stokes' shift spectrum (SSS), and reflectance spectrum (RS) of benign (N = 12) and malignant prostate tissues (N = 8) were investigated to discriminate the two types of tissues. The FES was done with the excitation at 325 nm only; SSS with Δλ = 70 and Δλ = 0, the latter being equivalent to reflectance spectra. Of the three modes of spectra, SSS with Δλ = 70 nm showed the best discrimination. There were four important bands, one at 280 nm (due to tryptophan); 320 nm (due to elastin & tryptophan); 355 and 385 (due to NADH) and 440 nm (due to flavin). From the relative intensities of these bands, three ratios were evaluated. Similarly another two ratios were obtained from reflectance spectra and one more from FES. Thus, there are 6 ratio parameters which represent the relative concentration of tryptophan, elastin, nicotinamide adenine dinucleotide (NADH), and flavin. A statistical analysis showed that benign and malignant tissues could be classified with accuracy greater than 90%. This report is only for in vitro analysis; but employing optical fiber, this can be extended to in vivo analysis too, so that benign tumor could be distinguished without surgery.

  19. [Study on the characters of phytoplankton chlorophyll fluorescence excitation spectra based on fourth-derivative].

    PubMed

    Lu, Lu; Su, Rong-Guo; Wang, Xiu-Lin; Zhu, Chen-Jian

    2007-11-01

    Chlorophyll fluorescence excitation spectra of six phytoplankton species, belonging to Bacillariophyta and Dinophyta, were dealt by fourth-derivative analysis with the Matlab program. The results show that between 350 nm and 550 nm six fluorescence peaks were found in the fourth-derivative spectra, which are representatives of non-pigments, chlorophylls and carotenoides respectively. The method makes Bacillariophyta and Dinophyta more distinguishable when the fourth-derivative spectra are compared with the chlorophyll fluorescence excitation spectra. It can be used not only to discriminate the two groups of algaes, but also to reduce the effect of noise. The fluorescence peaks in the fourth-derivative spectra are proved to be stable.

  20. [The Establishment of the Method of the Fiber Optic Chemical Sensor Synchronous Absorption-Fluorescence].

    PubMed

    Zhang Li-hua; Iburaim, Arkin

    2016-03-01

    A new method of simultaneously measuring fiber-optic chemical sensor absorption spectrum and fluorescence spectrum is established. Make synchronous absorption-fluorescence cuvette, establish synchronous absorption-fluorescence spectrometry instrumentation combined by fiber optic chemical sensor technology, measure the synchronous absorption-fluorescence spectrums of solutions of rhodamine B, vitamin B2 and vitamin B6, compared by absorption spectroscopy measured by traditional UV-Visible photometric method and fluorescence spectroscopy measured by traditional fluorescence method. Synchronous absorption-fluorescence method measure absorption spectrums and fluorescence spectrums the same to traditional photometric and fluorescence spectroscopy of rhodamine B, vitamin B2 and vitamin B6. The maximum wavelength of fluorescence intensity method has high accuracy relatively compared with fluorescence, but the maximum wavelength of absorption has a slight deviation. Synchronous absorption-fluorescence method means simultaneously measure the absorption spectrums and fluorescence spectrums of the fluorescent substance, making two spectrums to one. The method measured the maximum emission wavelength with high accuracy, though in measuring maximum absorption wavelength there is a slight deviation, but it is worth further studying. PMID:27400519

  1. Constraining The Reionization History With QSO Absorption Spectra

    NASA Astrophysics Data System (ADS)

    Gallerani, S.; Choudhury, T. R.; Ferrara, A.

    2006-08-01

    We use a semi-analytical approach to simulate absorption spectra of QSOs at high redshifts with the aim of constraining the cosmic reionization history. We consider two physically motivated and detailed reionization histories: (i) an Early Reionization Model (ERM) in which the intergalactic medium is reionized by PopIII stars at z~14, and (ii) a more standard Late Reionization Model (LRM) in which overlapping, induced by QSOs and normal galaxies, occurs at z~6. An example of simulated spectra is provided by FIG.1. From the analysis of current Lyα forest data at z<6, we conclude that it is impossible to disentangle the two scenarios, which fit equally well the observed Gunn-Peterson optical depth, flux probability distribution function and dark gap width distribution. At z>6, however, clear differences start to emerge which are best quantified by the dark gap width distribution. We find that 35 (zero) per cent of the lines of sight within 5.750Å in the rest frame of the QSO if re-ionization is not (is) complete at z>~6 (FIG.2). Similarly, the ERM predicts peaks of width ~1Å in 40 per cent of the lines of sight in the redshift range 6.0-6.6; in the same range, LRM predicts no peaks of width >0.8Å (FIG.3). We conclude that the dark gap and peak width statistics represent superb probes of cosmic reionization if about ten QSOs can be found at z>6.

  2. Investigation of fluorescence spectra disturbances influencing the classification performance of fluorescently labeled plastic flakes

    NASA Astrophysics Data System (ADS)

    Fomin, Petr; Brunner, Siegfried; Kargel, Christian

    2013-04-01

    The recycling of plastic products becomes increasingly attractive not only from an environmental point of view, but also economically. For recycled (engineering) plastic products with the highest possible quality, plastic sorting technologies must provide clean and virtually mono-fractional compositions from a mixture of many different types of (shredded) plastics. In order to put this high quality sorting into practice, the labeling of virgin plastics with specific fluorescent markers at very low concentrations (ppm level or less) during their manufacturing process is proposed. The emitted fluorescence spectra represent "optical fingerprints" - each being unique for a particular plastic - which we use for plastic identification and classification purposes. In this study we quantify the classification performance using our prototype measurement system and 15 different plastic types when various influence factors most relevant in practice cause disturbances of the fluorescence spectra emitted from the labeled plastics. The results of these investigations help optimize the development and incorporation of appropriate fluorescent markers as well as the classification algorithms and overall measurement system in order to achieve the lowest possible classification error rates.

  3. Absorption and Transport of Fluorescent Brighteners by Microorganisms

    PubMed Central

    Darken, Marjorie A.

    1962-01-01

    The absorption of brighteners by living cells and their transport to subsequent growth is described. Brighteners are highly fluorescent, ultraviolet-absorbing compounds which appear to be essentially nontoxic, stable biological markers. They have been effectively absorbed by growing cultures of bacteria, yeasts, actinomycetes, and higher fungi, with active growth centers evidencing the greatest flourescence. Images FIG. 2 FIG. 3 FIG. 4 FIG. 5 FIG. 6 FIG. 7 FIG. 8 FIG. 9 FIG. 10-11 PMID:14025111

  4. An Inverse Modeling Approach to Estimating Phytoplankton Pigment Concentrations from Phytoplankton Absorption Spectra

    NASA Technical Reports Server (NTRS)

    Moisan, John R.; Moisan, Tiffany A. H.; Linkswiler, Matthew A.

    2011-01-01

    Phytoplankton absorption spectra and High-Performance Liquid Chromatography (HPLC) pigment observations from the Eastern U.S. and global observations from NASA's SeaBASS archive are used in a linear inverse calculation to extract pigment-specific absorption spectra. Using these pigment-specific absorption spectra to reconstruct the phytoplankton absorption spectra results in high correlations at all visible wavelengths (r(sup 2) from 0.83 to 0.98), and linear regressions (slopes ranging from 0.8 to 1.1). Higher correlations (r(sup 2) from 0.75 to 1.00) are obtained in the visible portion of the spectra when the total phytoplankton absorption spectra are unpackaged by multiplying the entire spectra by a factor that sets the total absorption at 675 nm to that expected from absorption spectra reconstruction using measured pigment concentrations and laboratory-derived pigment-specific absorption spectra. The derived pigment-specific absorption spectra were further used with the total phytoplankton absorption spectra in a second linear inverse calculation to estimate the various phytoplankton HPLC pigments. A comparison between the estimated and measured pigment concentrations for the 18 pigment fields showed good correlations (r(sup 2) greater than 0.5) for 7 pigments and very good correlations (r(sup 2) greater than 0.7) for chlorophyll a and fucoxanthin. Higher correlations result when the analysis is carried out at more local geographic scales. The ability to estimate phytoplankton pigments using pigment-specific absorption spectra is critical for using hyperspectral inverse models to retrieve phytoplankton pigment concentrations and other Inherent Optical Properties (IOPs) from passive remote sensing observations.

  5. Inner filter effect and the onset of concentration dependent red shift of synchronous fluorescence spectra.

    PubMed

    Tarai, Madhumita; Mishra, Ashok Kumar

    2016-10-12

    The phenomenon of concentration dependent red shift, often observed in synchronous fluorescence spectra (SFS) of monofluorophoric as well as multifluorophoric systems at high chromophore concentrations, is known to have good analytical advantages. This was previously understood in terms of large inner filter effect (IFE) through the introduction of a derived absorption spectral profile that closely corresponds to the SFS profile. Using representative monofluorophoric and multifluorophoric systems, it is now explained how the SF spectral maximum changes with concentration of the fluorophore. For dilute solutions of monofluorophores the maximum is unchanged as expected. It is shown here that the onset of red shift of SFS maximum of both the mono as well as the multifluorophoric systems must occur at the derived absorption spectral parameter value of 0.32 that corresponds to the absorbance value of 0.87. This value is unique irrespective of the nature of the fluorophore under study. For monofluorophoric systems, the wavelength of derived absorption spectral maximum and the wavelength of synchronous fluorescence spectral maximum closely correspond with each other in the entire concentration range. In contrast, for multifluorophoric systems like diesel and aqueous humic acid, large deviations were noted that could be explained as to be due to the presence of non-fluorescing chromophores in the system. This work bridges the entire fluorophore concentration range over which the red shift of SFS maximum sets in; and in the process it establishes the importance of the derived absorption spectral parameter in understanding the phenomenon of concentration dependent red shift of SFS maximum.

  6. Inner filter effect and the onset of concentration dependent red shift of synchronous fluorescence spectra.

    PubMed

    Tarai, Madhumita; Mishra, Ashok Kumar

    2016-10-12

    The phenomenon of concentration dependent red shift, often observed in synchronous fluorescence spectra (SFS) of monofluorophoric as well as multifluorophoric systems at high chromophore concentrations, is known to have good analytical advantages. This was previously understood in terms of large inner filter effect (IFE) through the introduction of a derived absorption spectral profile that closely corresponds to the SFS profile. Using representative monofluorophoric and multifluorophoric systems, it is now explained how the SF spectral maximum changes with concentration of the fluorophore. For dilute solutions of monofluorophores the maximum is unchanged as expected. It is shown here that the onset of red shift of SFS maximum of both the mono as well as the multifluorophoric systems must occur at the derived absorption spectral parameter value of 0.32 that corresponds to the absorbance value of 0.87. This value is unique irrespective of the nature of the fluorophore under study. For monofluorophoric systems, the wavelength of derived absorption spectral maximum and the wavelength of synchronous fluorescence spectral maximum closely correspond with each other in the entire concentration range. In contrast, for multifluorophoric systems like diesel and aqueous humic acid, large deviations were noted that could be explained as to be due to the presence of non-fluorescing chromophores in the system. This work bridges the entire fluorophore concentration range over which the red shift of SFS maximum sets in; and in the process it establishes the importance of the derived absorption spectral parameter in understanding the phenomenon of concentration dependent red shift of SFS maximum. PMID:27662765

  7. Infrared absorption spectra of various doping states in cuprate superconductors

    SciTech Connect

    Yonemitsu, K.; Bishop, A.R.; Lorenzana, J.

    1992-02-01

    Doping states in a two-dimensional three-band extended Peierls-Hubbard model was investigated within inhomogeneous Hartree-Fock and random phase approximation. They are very sensitive to small changes of interaction parameters and their distinct vibrational and optical absorption spectra can be used to identify different doping states. For electronic parameters relevant to cuprate superconductors, as intersite electron-phonon interaction strength increases, the doping state changes from a Zhang-Rice state to a covalent molecular singlet state accompanied by local quenching of the Cu magnetic moment and large local lattice distortion in an otherwise undistorted antiferromagnetic background. In a region where both intersite electron-phonon interaction and on-site electron-electron repulsion are large, we obtain new stable global phases including a bond-order-wave state and a mixed state of spin-Peierls bonds and antiferromagnetic Cu spins, as well as many metastable states. Doping in the bond-order-wave region induces separation of spin and charge. 9 refs.

  8. Infrared absorption spectra of various doping states in cuprate superconductors

    SciTech Connect

    Yonemitsu, K.; Bishop, A.R. ); Lorenzana, J. )

    1992-01-01

    Doping states in a two-dimensional three-band extended Peierls-Hubbard model was investigated within inhomogeneous Hartree-Fock and random phase approximation. They are very sensitive to small changes of interaction parameters and their distinct vibrational and optical absorption spectra can be used to identify different doping states. For electronic parameters relevant to cuprate superconductors, as intersite electron-phonon interaction strength increases, the doping state changes from a Zhang-Rice state to a covalent molecular singlet state accompanied by local quenching of the Cu magnetic moment and large local lattice distortion in an otherwise undistorted antiferromagnetic background. In a region where both intersite electron-phonon interaction and on-site electron-electron repulsion are large, we obtain new stable global phases including a bond-order-wave state and a mixed state of spin-Peierls bonds and antiferromagnetic Cu spins, as well as many metastable states. Doping in the bond-order-wave region induces separation of spin and charge. 9 refs.

  9. Molecular structures and absorption spectra assignment of corrole NH tautomers.

    PubMed

    Beenken, Wichard; Presselt, Martin; Ngo, Thien H; Dehaen, Wim; Maes, Wouter; Kruk, Mikalai

    2014-02-01

    The individual absorption spectra of the two NH tautomers of 10-(4,6-dichloropyrimidin-5-yl)-5,15-dimesitylcorrole are assigned on the basis of the Gouterman four-orbital model and a quantum chemical TD-DFT study. The assignment indicates that the red-shifted T1 tautomer is the one with protonated pyrrole nitrogen atoms N(21), N(22) and N(23), whereas the blue-shifted T2 tautomer has pyrrole nitrogen atoms N(21), N(22) and N(24) protonated. A wave-like nonplanar distortion of the macrocycle in the ground state is found for both NH tautomers, with the wave axis going through the pyrroles containing N(22) and N(24). The 7C plane determined by the least-squares distances to the carbon atoms C1, C4, C5, C6, C9, C16, and C19 is suggested as a mean corrole macrocycle plane for the analysis of out-of-plane distortions. The magnitude of these distortions is distinctly different for the two NH tautomers, leading to substantial perturbations of their acid-base properties, which are rationalized by the interplay of the degree of out-of-plane distortion of the macrocycle as a whole and the tendency of the pyrrole nitrogen atoms toward pyramidalization, with the former leading to a basicity increase whereas the latter enhances the acidity.

  10. UV optical absorption spectra analysis of spodumene crystals from Brazil

    NASA Astrophysics Data System (ADS)

    Isotani, Sadao; Watari, Kazunori; Mizukami, Akiyoshi; Bonventi, Waldemar; Ito, Amando Siuiti

    2007-04-01

    The spectral decomposition analysis was applied to the optical absorption spectra of spodumene crystals from the Brazilian eastern pegmatitic province. The analyzed samples were natural, treated at 400 °C for 24 h and those irradiated with γ rays of 60Co with doses up to 5 MGy. The attributions of the lines were made taking in account highly accurate quantum mechanical calculations. The heated sample had only three lines, which were not affected by irradiation. One of them at 7.58 eV was attributed to an oxygen vacancy defect and the other two at 5.07 and 4.64 eV to a peroxy-type defect. The analysis of the growth of the lines with the irradiation showed that they belong to two groups of defects. The first group of lines at 4.2, 5.3 and 5.9 eV was attributed to a silanone-type defect. The other group of lines at 1.36, 2.0, 2.6, 3.6 and 5.0 eV was attributed to a type of Mn 3+ defect. The natural and irradiated samples also showed a line at 2.3 eV, which was attributed to another type of diamagnetic Mn 3+ defect.

  11. Correlation of molecular structure with fluorescence spectra in rare earth chelates. I.

    NASA Technical Reports Server (NTRS)

    Bjorklund, S.; Degnan, J.; Filipescu, N.; Mcavoy, N.

    1968-01-01

    Rare earth chelates fluorescence spectra correlation with molecular structure, analyzing emission spectrum internal Stark splitting of tetramethylammonium tetrakis /dibenzoylmethido/europate microcrystals

  12. Compact characterization of liquid absorption and emission spectra using linear variable filters integrated with a CMOS imaging camera

    PubMed Central

    Wan, Yuhang; Carlson, John A.; Kesler, Benjamin A.; Peng, Wang; Su, Patrick; Al-Mulla, Saoud A.; Lim, Sung Jun; Smith, Andrew M.; Dallesasse, John M.; Cunningham, Brian T.

    2016-01-01

    A compact analysis platform for detecting liquid absorption and emission spectra using a set of optical linear variable filters atop a CMOS image sensor is presented. The working spectral range of the analysis platform can be extended without a reduction in spectral resolution by utilizing multiple linear variable filters with different wavelength ranges on the same CMOS sensor. With optical setup reconfiguration, its capability to measure both absorption and fluorescence emission is demonstrated. Quantitative detection of fluorescence emission down to 0.28 nM for quantum dot dispersions and 32 ng/mL for near-infrared dyes has been demonstrated on a single platform over a wide spectral range, as well as an absorption-based water quality test, showing the versatility of the system across liquid solutions for different emission and absorption bands. Comparison with a commercially available portable spectrometer and an optical spectrum analyzer shows our system has an improved signal-to-noise ratio and acceptable spectral resolution for discrimination of emission spectra, and characterization of colored liquid’s absorption characteristics generated by common biomolecular assays. This simple, compact, and versatile analysis platform demonstrates a path towards an integrated optical device that can be utilized for a wide variety of applications in point-of-use testing and point-of-care diagnostics. PMID:27389070

  13. Compact characterization of liquid absorption and emission spectra using linear variable filters integrated with a CMOS imaging camera.

    PubMed

    Wan, Yuhang; Carlson, John A; Kesler, Benjamin A; Peng, Wang; Su, Patrick; Al-Mulla, Saoud A; Lim, Sung Jun; Smith, Andrew M; Dallesasse, John M; Cunningham, Brian T

    2016-01-01

    A compact analysis platform for detecting liquid absorption and emission spectra using a set of optical linear variable filters atop a CMOS image sensor is presented. The working spectral range of the analysis platform can be extended without a reduction in spectral resolution by utilizing multiple linear variable filters with different wavelength ranges on the same CMOS sensor. With optical setup reconfiguration, its capability to measure both absorption and fluorescence emission is demonstrated. Quantitative detection of fluorescence emission down to 0.28 nM for quantum dot dispersions and 32 ng/mL for near-infrared dyes has been demonstrated on a single platform over a wide spectral range, as well as an absorption-based water quality test, showing the versatility of the system across liquid solutions for different emission and absorption bands. Comparison with a commercially available portable spectrometer and an optical spectrum analyzer shows our system has an improved signal-to-noise ratio and acceptable spectral resolution for discrimination of emission spectra, and characterization of colored liquid's absorption characteristics generated by common biomolecular assays. This simple, compact, and versatile analysis platform demonstrates a path towards an integrated optical device that can be utilized for a wide variety of applications in point-of-use testing and point-of-care diagnostics. PMID:27389070

  14. Compact characterization of liquid absorption and emission spectra using linear variable filters integrated with a CMOS imaging camera

    NASA Astrophysics Data System (ADS)

    Wan, Yuhang; Carlson, John A.; Kesler, Benjamin A.; Peng, Wang; Su, Patrick; Al-Mulla, Saoud A.; Lim, Sung Jun; Smith, Andrew M.; Dallesasse, John M.; Cunningham, Brian T.

    2016-07-01

    A compact analysis platform for detecting liquid absorption and emission spectra using a set of optical linear variable filters atop a CMOS image sensor is presented. The working spectral range of the analysis platform can be extended without a reduction in spectral resolution by utilizing multiple linear variable filters with different wavelength ranges on the same CMOS sensor. With optical setup reconfiguration, its capability to measure both absorption and fluorescence emission is demonstrated. Quantitative detection of fluorescence emission down to 0.28 nM for quantum dot dispersions and 32 ng/mL for near-infrared dyes has been demonstrated on a single platform over a wide spectral range, as well as an absorption-based water quality test, showing the versatility of the system across liquid solutions for different emission and absorption bands. Comparison with a commercially available portable spectrometer and an optical spectrum analyzer shows our system has an improved signal-to-noise ratio and acceptable spectral resolution for discrimination of emission spectra, and characterization of colored liquid’s absorption characteristics generated by common biomolecular assays. This simple, compact, and versatile analysis platform demonstrates a path towards an integrated optical device that can be utilized for a wide variety of applications in point-of-use testing and point-of-care diagnostics.

  15. Surface extended x-ray absorption fine structure of low-Z absorbates using fluorescence detection

    SciTech Connect

    Stoehr, J.; Kollin, E.B.; Fischer, D.A.; Hastings, J.B.; Zaera, F.; Sette, F.

    1985-05-01

    Comparison of x-ray fluorescence yield (FY) and electron yield surface extended x-ray absorption fine structure spectra above the S K-edge for c(2 x 2) S on Ni(100) reveals an order of magnitude higher sensitivity of the FY technique. Using FY detection, thiophene (C/sub 4/H/sub 4/S) chemisorption on Ni(100) is studied with S coverages down to 0.08 monolayer. The molecule dissociates at temperatures as low as 100K by interaction with fourfold hollow Ni sites. Blocking of these sites by oxygen leaves the molecule intact.

  16. A Passive Method for Detecting Vegetation Stress from Orbit: Chlorophyll Fluorescence Spectra from Fraunhofer Lines

    NASA Technical Reports Server (NTRS)

    Theisen, Arnold F.

    2000-01-01

    Solar-stimulated chlorophyll fluorescence measured with the Fraunhofer line depth method has correlated well with vegetation stress in previous studies. However, the instruments used in those studies were limited to a single solar absorption line (e.g. 656.3 nm), obviating the red/far-red ratio (R/FR) method. Optics and detector technology have reached the level whereby multiple, very narrow Fraunhofer lines are resolvable. Thirteen such lines span the visible spectrum in the red to far-red region where chlorophyll fluorescence occurs. Fluorescence intensities at the 13 Fraunhofer line wavelengths were used to model emission spectra. The source data were collected for summer and fall bean crops (Phaseolus vulgaris L.) subjected to various levels of nitrogen fertilization. The intensities were adjusted to account for Fraunhofer line depth and atmospheric transmittance. Multiple R/FR fluorescence ratios, calculated from the modeled fluorescence spectra, correlated strongly with leaf chlorophyll concentration and well with applied nitrogen. The ratio yielding the best correlation with chlorophyll utilized red fluorescence at the 694.5 nm Fraunhofer line and farred fluorescence at the 755.6 nm Fraunhofer line. Twenty R/FR ratios, each evaluated for the maximum differential between low and high (optimal) nitrogen treatments, ranked higher in some cases and lower in others, possibly related to the time of year the crops were grown and the stage of growth of the crops. Ratios with 728.9 nm and 738.9 nm in the denominator consistently ranked in the lowest and next lowest quartile, respectively. Ratios of the 656.3 nm Fraunhofer line and the 755.6 nm line consistently ranked highest for the summer crop. Ratios with 755.6 nm in the denominator ranked in the upper quartile for 10 out of 12 measurement dates. Differences in ratio ranking indicate that physiological conditions may be estimated using selected ratios of Fraunhofer lines within the context of R/FR analysis. A

  17. Constraining the reionization history with QSO absorption spectra

    NASA Astrophysics Data System (ADS)

    Gallerani, S.; Choudhury, T. Roy; Ferrara, A.

    2006-08-01

    We use a semi-analytical approach to simulate absorption spectra of QSOs at high redshifts with the aim of constraining the cosmic reionization history. We consider two physically motivated and detailed reionization histories: (i) an early reionization model (ERM) in which the intergalactic medium is reionized by Pop III stars at z ~ 14, and (ii) a more standard late reionization model (LRM) in which overlapping, induced by QSOs and normal galaxies, occurs at z ~ 6. From the analysis of current Lyα forest data at z < 6, we conclude that it is impossible to disentangle the two scenarios, which fit equally well the observed Gunn-Peterson optical depth, flux probability distribution function and dark gap width distribution. At z > 6, however, clear differences start to emerge which are best quantified by the dark gap and peak width distributions. We find that 35 (0) per cent of the lines of sight (LOS) within 5.7 < z < 6.3 show dark gaps of widths >50Å in the rest frame of the QSO if reionization is not (is) complete at z >~ 6. Similarly, the ERM predicts peaks of width ~1Å in 40 per cent of the LOS in the redshift range 6.0-6.6 in the same range, LRM predicts no peaks of width >0.8Å. We conclude that the dark gap and peak width statistics represent superb probes of cosmic reionization if about ten QSOs can be found at z > 6. We finally discuss strengths and limitations of our method.

  18. Deriving chlorophyll fluorescence emissions of vegetation canopies from high resolution field reflectance spectra

    NASA Astrophysics Data System (ADS)

    Middleton, Elizabeth M.; Corp, Lawrence A.; Daughtry, Craig S.; Entcheva Campbell, Petya K.; Butcher, L. Maryn

    2005-11-01

    Fluorescence of foliage in the laboratory has proven more rigorous than reflectance for correlation to plant physiology. Especially useful are emissions produced from two stable red and far-red chlorophyll fluorescence (ChlF) peaks centered at 685 nm and 735 nm. Methods have been developed elsewhere to extract steady state solar induced fluorescence (SIF) from apparent reflectance of vegetation canopies/landscapes using the Fraunhofer Line Depth (FLD) principal. Our study utilized these methods in conjunction with field-acquired high spectral resolution canopy reflectance spectra obtained in 2004 and 2005 over corn crops and small tree plots of three deciduous species (red maple, tulip poplar, sweet gum). Leaf level measurements were also made of foliage which included ChlF, photosynthesis, and leaf constituents (photosynthetic pigment, carbon (C), and nitrogen (N) contents). As part of ongoing experiments, measurements were made on N application plots within corn (280, 140, 70, and 0 kg N/ha) and tree (0, 37.5, 75, 112.5, 150 kg N /ha) sites at the USDA/Agriculture Research Service in Beltsville, MD. SIF intensities for ChlF were derived directly from canopy reflectance spectra in specific narrow- band regions associated with atmospheric oxygen absorption features centered at 688 and 760 nm. The red/far-red SIF ratio (SIFratio) derived from these field reflectance spectra successfully discriminated foliar pigment ratios altered by N application rates in both corn crops. This ratio was also positively correlated to the C/N ratio at leaf and canopy levels, for the available corn data (e.g., 2004). No consistent N treatment or species differences in SIF were detected in the tree foliage, but additional 2005 data are forthcoming. This study has relevance to future passive satellite remote sensing approaches to monitoring C dynamics from space.

  19. [Decomposition of hemoglobin UV absorption spectrum into absorption spectra of prosthetic group and apoprotein by means of an additive model].

    PubMed

    Lavrinenko, I A; Vashanov, G A; Artyukhov, V G

    2015-01-01

    The decomposition pathways of hemoglobin UV absorption spectrum into the absorption spectra of the protein and non-protein components are proposed and substantiated by means of an additive model. We have established that the heme component has an absorption band with a maximum at λ(max) = 269.2 nm (ε = 97163) and the apoprotein component has an absorption band with a maximum at λ(max) = 278.4 nm (ε = 48669) for the wavelength range from 240.0 to 320.0 nm. An integral relative proportion of absorption for the heme fraction (78.8%) and apoprotein (21.2%) in the investigating wavelength range is defined.

  20. The fluorescence action spectra of some saturated hydrocarbon liquids for excitation energies above and below their ionization thresholds

    SciTech Connect

    Ostafin, A.E.; Lipsky, S. )

    1993-04-01

    Fluorescence action spectra have been obtained for the neat liquids, [ital cis]-decalin, [ital trans]-decalin, bicyclohexyl, cyclohexane, methylcyclohexane, isobutylcyclohexane, 2,3,4-trimethylpentane, 2,3-dimethylbutane, 3-methylhexane, 3-methylpentane, [ital n]-decane, [ital n]-dodecane, and [ital n]-pentadecane at excitation energies, [epsilon], ranging from their absorption onsets (at ca. 7 eV) to 10.3 eV. For all compounds, with the exception of [ital cis]-decalin, the fluorescence quantum yield is observed to monotonically decline with increasing [epsilon], reaching a minimum value at an energy, [epsilon][sub [ital m

  1. Preliminary Analysis of Apparent Reflectance Spectra at SIFLEX: Observation of Fluorescence Effects

    NASA Astrophysics Data System (ADS)

    Miller, J.; Alonso, L.; Moreno, J.; Moya, I.; Garcia, J.; Pedros, R.

    (lichen and moss), and (d) sampling of typical needle reflectance transmittance spectra to be associated with biochemical sampling of needle pigments. These measurements of the Sodankyla canopy attempt to capture the complexity of site, to facilitate potential modelling and interpretation of the combined fluorescence and spectral radiance signals. Spectral Radiance and Reflectance Measurements Analysis: An ASD-FR field spectroradiometer was used at the site to collect spectral radiance data (and reflectance after reference to a Spectralon panel) normally at 15 minute intervals throughout the daylight hours from a tower overlooking specific Scot~@~Ys Pine crowns within the 25 m square area, which were also the target of continuous diurnal fluorescence measurements. Occasional additional spectral measurements were carried out in conjunction with the fluorescence data collection by targeting specific shoots with the ASD-FR and within the canopy using the Optronic 754-O-PMT spectroradiometer set to measure the O2 760 band vertical radiance distribution at high spectral resolution. Preliminary Analysis Results: Although analysis of data must be considered very preliminary at this stage (only days after the end of the field campaign) some early results show promise with respect to demonstrating inferences of the small fluorescence signal in the presence of the dominant solar-scattered radiance signal. Two initial protocols for analysis of the ASD-FR spectral radiance and reflectance data were explored on site. These were based on: (1) absorption line in-filling, and (2) derivative spectroscopy of the red edge reflectance region. In the first analysis protocol an estimate of the fluorescence radiance amplitude at 760 nm is based on the in-filling of the atmospheric O2 band using spectral radiance data from the target compared to that obtained nearly-simultaneously from a non- fluorescing white reference target. The advantage of this first approach is that it is relatively

  2. Fluorescence Excitation-Emission Matrix Regional Integration to Quantify Spectra for Dissolved Organic Matter

    USGS Publications Warehouse

    Chen, W.; Westerhoff, P.; Leenheer, J.A.; Booksh, K.

    2003-01-01

    Excitation-emission matrix (EEM) fluorescence spectroscopy has been widely used to characterize dissolved organic matter (DOM) in water and soil. However, interpreting the >10,000 wavelength-dependent fluorescence intensity data points represented in EEMs has posed a significant challenge. Fluorescence regional integration, a quantitative technique that integrates the volume beneath an EEM, was developed to analyze EEMs. EEMs were delineated into five excitation-emission regions based on fluorescence of model compounds, DOM fractions, and marine waters or freshwaters. Volumetric integration under the EEM within each region, normalized to the projected excitation-emission area within that region and dissolved organic carbon concentration, resulted in a normalized region-specific EEM volume (??i,n). Solid-state carbon nuclear magnetic resonance (13C NMR), Fourier transform infrared (FTIR) analysis, ultraviolet-visible absorption spectra, and EEMs were obtained for standard Suwannee River fulvic acid and 15 hydrophobic or hydrophilic acid, neutral, and base DOM fractions plus nonfractionated DOM from wastewater effluents and rivers in the southwestern United States. DOM fractions fluoresced in one or more EEM regions. The highest cumulative EEM volume (??T,n = ????i,n) was observed for hydrophobic neutral DOM fractions, followed by lower ??T,n values for hydrophobic acid, base, and hydrophilic acid DOM fractions, respectively. An extracted wastewater biomass DOM sample contained aromatic protein- and humic-like material and was characteristic of bacterial-soluble microbial products. Aromatic carbon and the presence of specific aromatic compounds (as indicated by solid-state 13C NMR and FTIR data) resulted in EEMs that aided in differentiating wastewater effluent DOM from drinking water DOM.

  3. Fluorescence spectra of bioaerosols exposed to ozone in a laboratory reaction chamber to simulate atmospheric processing

    NASA Astrophysics Data System (ADS)

    Pan, Yong-Le; Hill, Steven C.; Pinnick, Ronald G.; Santarpia, Joshua L.; Baker, Neal; Alvarez, Benjamin; Ratnesar-Shumate, Shanna; Cottrell, Brian; McKee, Laura

    2011-05-01

    Laboratory measurements demonstrating the effects of ozone on aerosolized B. thuringiensis, as revealed by fluorescence spectra, are reported. The fluorescence emission peak around 330 nm (excited at 263nm) decreases somewhat in intensity and becomes slightly blue-shifted. Further, the fluorescence emission around 400 nm-550 nm is less affected by the ozone than is the 330 nm (tryptophan) peak.

  4. Absorption and fluorescence of alexandrite and of titanium in sapphire and glass

    NASA Technical Reports Server (NTRS)

    Byvik, C. E.; Hess, R. V.; Buoncristiani, A. M.

    1985-01-01

    The fluorescence and absorption data for titanium in crystalline sapphire and titanium doped into two silicate and one phosphate glass structures are analyzed. It is observed that the Ti-doped silicate glass sample exhibits no absorption related to the Ti(III) ion, the Ti-doped phosphate glass is deep blue, the absorption line width of the glass samples are a factor of two larger than that of sapphire, and the absorption peak for the Ti in the glass shifted about 100 nm to the red from the Ti:sapphire absorption peak. This shift reveals that the Ti(III) ion is sensitive to the crystalline environment and not to the glass environment. The photoluminescence spectra for Ti-doped sapphire and alexandrite are compared. It is detected that the Ti:sapphire exhibits a broader spectrum than that for alexandrite with a peak at 750 nm. The three zero phonon transitions of Ti:Al2O3 at liquid nitrogen temperatures are studied.

  5. Interpretation of NO2 absorption in twilight sky spectra

    NASA Astrophysics Data System (ADS)

    McMahon, B. B.

    1984-07-01

    A multiple scattering model has been developed to calculate nitrogen dioxide (NO2) absorption in the light from the zenith sky during twilight. Model studies show that this absorption is not very sensitive to the atmospheric temperature profile or to tropospheric NO2. The model was used to interpret some ground-based measurements of NO2 sky absorption. Values for the total stratospheric column amount vary from 2 to 12 x 10 to the 15th molec/sq cm, and the mean altitude of the stratospheric concentration profile is around 35 km. These observations are in broad agreement with those of other workers.

  6. Fluorescence and UV/VIS absorption spectroscopy studies on polymer blend films for photovoltaics

    NASA Astrophysics Data System (ADS)

    van Stam, Jan; Lindqvist, Camilla; Hansson, Rickard; Ericsson, Leif; Moons, Ellen

    2015-08-01

    The quinoxaline-based polymer TQ1 (poly[2,3-bis-(3-octyloxyphenyl)quinoxaline-5,8-diyl-alt-thiophene-2,5- diyl]) is a promising candidate as electron donor in organic solar cells. In combination with the electron acceptor [6,6]- phenyl-C71- butyric acid methyl ester (PC70BM), TQ1 has resulted in solar cells with power conversion efficiencies of 7 %. We have studied TQ1 films, with and without PC70BM, spin-casted from different solvents, by fluorescence spectroscopy and UV/VIS absorption spectroscopy. We used chloroform (CF), chlorobenzene (CB), and odichlorobenzene (o-DCB) as solvents for the coating solutions and 1-chloronaphthalene (CN) as solvent additive. CN addition has been shown to enhance photo-conversion efficiency of these solar cells. Phase-separation causes lateral domain formation in the films and the domain size depends on the solvent . These morphological differences coincide with changes in the spectroscopic patterns of the films. From a spectroscopic point of view, TQ1 acts as fluorescent probe and PC70BM as quencher. The degree of fluorescence quenching is coupled to the morphology through the distance between TQ1 and PC70BM. Furthermore, if using a bad solvent for PC70BM, morphological regions rich in the fullerene yield emission characteristic for aggregated PC70BM. Clear differences were found, comparing the TQ1:PC70BM blend films casted from different solvents and at different ratios between the donor and acceptor. The morphology also influences the UV/VIS absorption spectra, yielding further information on the composition. The results show that fluorescence and UV/VIS absorption spectroscopy can be used to detect aggregation in blended films and that these methods extend the morphological information beyond the scale accessible with microscopy.

  7. Absorption spectra of graphene nanoribbons in a composite magnetic field

    NASA Astrophysics Data System (ADS)

    Li, T. S.; Wu, M. F.; Hsieh, C. T.

    2015-10-01

    The low-frequency optical absorption properties of graphene nanoribbons in a composite magnetic field are investigated by using the gradient approximation. The spectral function exhibits symmetric delta-function like prominent peaks structure in a uniform magnetic field, and changes to asymmetric square-root divergent peaks structure when subjecting to a composite field. These asymmetric divergent peaks can be further classified into principal and secondary peaks. The spectral intensity and frequency of the absorption peaks depend sensitively on the strength and modulation period of the composite field. The transition channels of the absorption peaks are also analyzed. There exists an optical selection rule which is caused by the orthogonal properties of the sublattice wave functions. The evolution of the spectral frequency of the absorption peaks with the field strength is explored.

  8. [AO distribution and fluorescence spectra in myoblasts and single muscle fibres].

    PubMed

    Beliaeva, T N; Krolenko, S A; Leont'eva, E A; Mozhenok, T P; Salova, A V; Faddeeva, M D

    2009-01-01

    Using spectral scanning regime of Leica TCS SL confocal microscope, acridine orange (AO) fluorescence spectra in nuclei and cytoplasms of living myoblasts L6J1 and frog single muscle fibres have been studied. AO fluorescence spectra in salt solutions dependent on free AO concentrations and in AO complexes with DNA have also been obtained for comparison. Myoblasts nuclei fluoresced in green spectral region with maximum at approximately 530 nm (corresponding AO monomers fluorescence), nucleoli fluoresced most brightly. Nuclear chromatin fluoresced not uniformly in these cells. We saw similar to myoblasts AO emission in nucleoli and nuclei of frog single muscle fibres. The uniformed weak green fluorescence was observed for myoblast cytoplasm. As to the muscle fibres sarcoplasm, we saw also AO green fluorescence in A-discs. In myoblasts and muscle fibre cytoplasm we saw the fluorescent red, yellow and green granules which were acidic organelles. The comparison of AO fluorescence spectra in living cells with fluorescence spectra of different AO concentrations and complexes of AO with DNA in buffer solutions allows estimation of AO concentration in acidic granules which is of interest in the investigation of cellular organelles functions in the processes of intracellular transport, adaptation, apoptosis and a number of pathological conditions.

  9. Assignment of benzodiazepine UV absorption spectra by the use of photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Khvostenko, O. G.; Tzeplin, E. E.; Lomakin, G. S.

    2002-04-01

    Correlations between singlet transition energies and energy gaps of corresponding pairs of occupied and unoccupied molecular orbitals were revealed in a series of benzodiazepines. The occupied orbital energies were taken from the photoelectron spectra of the compound investigated, the unoccupied ones were obtained from MNDO/d calculations, and the singlet energies were taken from the UV absorption spectra. The correspondence of the singlet transitions to certain molecular orbitals was established using MNDO/d calculations and comparing between UV and photoelectron spectra. It has been concluded that photoelectron spectroscopy can be applied for interpretation of UV absorption spectra of various compounds on the basis of similar correlations.

  10. Effects of lowly ionized ions on silicon K-shell absorption spectra

    NASA Astrophysics Data System (ADS)

    Wei, H. G.; Shi, J. R.; Liang, G. Y.; Wang, F. L.; Zhong, J. Y.; Zhao, G.

    2016-05-01

    Context. In both astrophysical and laboratory plasmas, K-shell absorption spectra have become powerful diagnostic tools to investigate electron density and temperature. These spectra are also widely used to verify the opacity codes in laboratory settings. Aims: We report the effects of the low ionization silicon ions, namely from Si I to Si V, which have rarely been considered in previous models, on the K-shell silicon absorption spectra. Methods: The Si K-shell atomic data were calculated with the flexible atomic code, which is a fully relativistic atomic program with configuration interaction taken into consideration. Detailed level accounting models were employed to calculate the absorption spectra. Results: We calculate the Si absorption spectra in local thermodynamic equilibrium conditions with temperature and density ranges of 20-70 eV and ~1020 cm-3 to ~1022 cm-3, respectively, and show the contributions of the lowly ionized ions to the K-shell absorption spectra of silicon. We also investigate the effects of the different atomic data on the absorption spectra. We find good agreement between our results and these from OPLIB. Conclusions: We find that the contributions from these lowly ionized ions cannot be neglected at relative low temperatures. Accurate experimental measurements are needed to benchmark the theoretical calculations.

  11. Protonation effects on the UV/Vis absorption spectra of imatinib: A theoretical and experimental study

    NASA Astrophysics Data System (ADS)

    Grante, Ilze; Actins, Andris; Orola, Liana

    2014-08-01

    An experimental and theoretical investigation of protonation effects on the UV/Vis absorption spectra of imatinib showed systematic changes of absorption depending on the pH, and a new absorption band appeared below pH 2. These changes in the UV/Vis absorption spectra were interpreted using quantum chemical calculations. The geometry of various imatinib cations in the gas phase and in ethanol solution was optimized with the DFT/B3LYP method. The resultant geometries were compared to the experimentally determined crystal structures of imatinib salts. The semi-empirical ZINDO-CI method was employed to calculate the absorption lines and electronic transitions. Our study suggests that the formation of the extra near-UV absorption band resulted from an increase of imatinib trication concentration in the solution, while the rapid increase of the first absorption maximum could be attributed to both the formation of imatinib trication and tetracation.

  12. Chlorophyll Fluorescence Emissions of Vegetation Canopies From High Resolution Field Reflectance Spectra

    NASA Technical Reports Server (NTRS)

    Middleton, E. M.; Corp, L. A.; Daughtry, C. S. T.; Campbell, P. K. Entcheva

    2006-01-01

    A two-year experiment was performed on corn (Zea mays L.) crops under nitrogen (N) fertilization regimes to examine the use of hyperspectral canopy reflectance information for estimating chlorophyll fluorescence (ChlF) and vegetation production. Fluorescence of foliage in the laboratory has proven more rigorous than reflectance for correlation to plant physiology. Especially useful are emissions produced from two stable red and far-red chlorophyll ChlF peaks centered at 685V10 nm and 735V5 nm. Methods have been developed elsewhere to extract steady state solar induced fluorescence (SF) from apparent reflectance of vegetation canopies/landscapes using the Fraunhofer Line Depth (FLD) principal. Our study utilized these methods in conjunction with field-acquired high spectral resolution canopy reflectance spectra obtained in 2004 and 2005 over corn crops, as part of an ongoing multi-year experiment at the USDA/Agriculture Research Service in Beltsville, MD. A spectroradiometer (ASD-FR Fieldspec Pro, Analytical Spectral Devices, Inc., Boulder, CO) was used to measure canopy radiances 1 m above plant canopies with a 22deg field of view and a 0deg nadir view zenith angle. Canopy and plant measurements were made at the R3 grain fill reproductive stage on 3-4 replicate N application plots provided seasonal inputs of 280, 140, 70, and 28 kg N/ha. Leaf level measurements were also made which included ChlF, photosynthesis, and leaf constituents (photosynthetic pigment, carbon (C), and N contents). Crop yields were determined at harvest. SIF intensities for ChlF were derived directly from canopy reflectance spectra in specific narrowband regions associated with atmospheric oxygen absorption features centered at 688 and 760 nm. The red/far-red S F ratio derived from these field reflectance spectra successfully discriminated foliar pigment levels (e.g., total chlorophyll, Chl) associated with N application rates in both corn crops. This canopy-level spectral ratio was also

  13. Resolution of heterogeneous fluorescence into component decay-associated excitation spectra. Application to subtilisins.

    PubMed

    Willis, K J; Szabo, A G; Drew, J; Zuker, M; Ridgeway, J M

    1990-02-01

    Direct and indirect methods are described to combine steady-state and picosecond time-resolved fluorescence decay data to generate decay-associated excitation spectra. The heterogeneous fluorescence from a fluorophore mixture that models protein fluorescence was resolved into individual component excitation spectra. The two methods were also used to determine the excitation spectra associated with each of the decay time components for the proteins subtilisin Carlsberg and BPN'. On the basis of associated spectra, the decay components of both proteins were assigned to individual (or groups of) emitting species. The two approaches used to generate the decay-associated excitation spectra are compared and their general application to protein fluorescence studies is discussed. PMID:2180489

  14. Modeling of fluorescence line-narrowed spectra in weakly coupled dimers in the presence of excitation energy transfer

    SciTech Connect

    Lin, Chen; Reppert, Mike; Feng, Ximao; Jankowiak, Ryszard

    2014-07-21

    This work describes simple analytical formulas to describe the fluorescence line-narrowed (FLN) spectra of weakly coupled chromophores in the presence of excitation energy transfer (EET). Modeling studies for dimer systems (assuming low fluence and weak coupling) show that the FLN spectra (including absorption and emission spectra) calculated for various dimers using our model are in good agreement with spectra calculated by: (i) the simple convolution method and (ii) the more rigorous treatment using the Redfield approach [T. Renger and R. A. Marcus, J. Chem. Phys. 116, 9997 (2002)]. The calculated FLN spectra in the presence of EET of all three approaches are very similar. We argue that our approach provides a simplified and computationally more efficient description of FLN spectra in the presence of EET. This method also has been applied to FLN spectra obtained for the CP47 antenna complex of Photosystem II reported by Neupane et al. [J. Am. Chem. Soc. 132, 4214 (2010)], which indicated the presence of uncorrelated EET between pigments contributing to the two lowest energy (overlapping) exciton states, each mostly localized on a single chromophore. Calculated and experimental FLN spectra for CP47 complex show very good qualitative agreement.

  15. Microwave-assisted synthesis of water-soluble, fluorescent gold nanoclusters capped with small organic molecules and a revealing fluorescence and X-ray absorption study

    NASA Astrophysics Data System (ADS)

    Helmbrecht, C.; Lützenkirchen-Hecht, D.; Frank, W.

    2015-03-01

    Colourless solutions of blue light-emitting, water-soluble gold nanoclusters (AuNC) were synthesized from gold colloids under microwave irradiation using small organic molecules as ligands. Stabilized by 1,3,5-triaza-7-phosphaadamantane (TPA) or l-glutamine (GLU), fluorescence quantum yields up to 5% were obtained. AuNC are considered to be very promising for biological labelling, optoelectronic devices and light-emitting materials but the structure-property relationships have still not been fully clarified. To expand the knowledge about the AuNC apart from their fluorescent properties they were studied by X-ray absorption spectroscopy elucidating the oxidation state of the nanoclusters' gold atoms. Based on curve fitting of the XANES spectra in comparison to several gold references, optically transparent fluorescent AuNC are predicted to be ligand-stabilized Au5+ species. Additionally, their near edge structure compared with analogous results of polynuclear clusters known from the literature discloses an increasing intensity of the feature close to the absorption edge with decreasing cluster size. As a result, a linear relationship between the cluster size and the X-ray absorption coefficient can be established for the first time.Colourless solutions of blue light-emitting, water-soluble gold nanoclusters (AuNC) were synthesized from gold colloids under microwave irradiation using small organic molecules as ligands. Stabilized by 1,3,5-triaza-7-phosphaadamantane (TPA) or l-glutamine (GLU), fluorescence quantum yields up to 5% were obtained. AuNC are considered to be very promising for biological labelling, optoelectronic devices and light-emitting materials but the structure-property relationships have still not been fully clarified. To expand the knowledge about the AuNC apart from their fluorescent properties they were studied by X-ray absorption spectroscopy elucidating the oxidation state of the nanoclusters' gold atoms. Based on curve fitting of the XANES

  16. Study on fluorescence spectra of thiamine, riboflavin and pyridoxine

    NASA Astrophysics Data System (ADS)

    Yang, Hui; Xiao, Xue; Zhao, Xuesong; Hu, Lan; Lv, Caofang; Yin, Zhangkun

    2016-01-01

    This paper presents the intrinsic fluorescence characteristics of vitamin B1, B2 and B6 measured with 3D fluorescence Spectrophotometer. Three strong fluorescence areas of vitamin B2 locate at λex/λem=270/525nm, 370/525nm and 450/525nm, one fluorescence areas of vitamin B1 locates at λex/λem=370/460nm, two fluorescence areas of vitamin B6 locate at λex/λem=250/370nm and 325/370nm were found. The influence of pH of solution to the fluorescence profile was also discussed. Using the PARAFAC algorithm, 10 vitamin B1, B2 and B6 mixed solutions were successfully decomposed, and the emission profiles, excitation profiles, central wavelengths and the concentration of the three components were retrieved precisely through about 5 iteration times.

  17. Applications of principal component analysis to breath air absorption spectra profiles classification

    NASA Astrophysics Data System (ADS)

    Kistenev, Yu. V.; Shapovalov, A. V.; Borisov, A. V.; Vrazhnov, D. A.; Nikolaev, V. V.; Nikiforova, O. Y.

    2015-12-01

    The results of numerical simulation of application principal component analysis to absorption spectra of breath air of patients with pulmonary diseases are presented. Various methods of experimental data preprocessing are analyzed.

  18. Determination of the major groups of phytoplankton pigments from the absorption spectra of total particulate matter

    NASA Technical Reports Server (NTRS)

    Hoepffner, Nicolas; Sathyendranath, Shubha

    1993-01-01

    The contributions of detrital particles and phytoplankton to total light absorption are retrieved by nonlinear regression on the absorption spectra of total particles from various oceanic regions. The model used explains more than 96% of the variance in the observed particle absorption spectra. The resulting absorption spectra of phytoplankton are then decomposed into several Gaussian bands reflecting absorption by phytoplankton pigments. Such a decomposition, combined with high-performance liquid chromatography data on phytoplankton pigment concentrations, allows the computation of specific absorption coefficients for chlorophylls a, b, and c and carotenoids. The spectral values of these in vivo absorption coefficients are then discussed, considering the effects of secondary pigments which were not measured quantitatively. We show that these coefficients can be used to reconstruct the absorption spectra of phytoplankton at various locations and depths. Discrepancies that do occur at some stations are explained in terms of particle size effect. These coefficients can be used to determine the concentrations of phytoplankton pigments in the water, given the absorption spectrum of total particles.

  19. [Analysis of three-dimensional fluorescence overlapping spectra using nonnegative matrix factorization].

    PubMed

    Yu, Xiao-Ya; Zhang, Yu-Jun; Yin, Gao-Fang; Zhao, Nan-Jing; Xiao, Xue; Zhang, Wei; Zhang, Rong; Lu, Chang-Hua; Liu, Wen-Qing

    2014-03-01

    The present paper primarily tests and verifies the effect of NMF in blind source separation of three-dimensional simulative fluorescence spectra, and then four different computational algorithms (multiplicative iterative; alternating least square; second order method; projected gradient algorithm) were used in three practical phenolic compounds (cresol, phenol, thymol) overlapping fluorescence spectra to find out which nonnegatively constrained algorithms is the most efficient for fluorescence spectra unmixing. The experiments demonstrate that four ways have the normalized residuals below 0.06%, and alternating least square (ALS) is the best at both convergence behavior and robustness. PMID:25208393

  20. Two-photon absorption spectra of a near-infrared 2-azaazulene polymethine dye: solvation and ground-state symmetry breaking.

    PubMed

    Hu, Honghua; Przhonska, Olga V; Terenziani, Francesca; Painelli, Anna; Fishman, Dmitry; Ensley, Trenton R; Reichert, Matthew; Webster, Scott; Bricks, Julia L; Kachkovski, Alexey D; Hagan, David J; Van Stryland, Eric W

    2013-05-28

    Polymethine dyes (PDs) with absorption bands in the near-infrared region undergo symmetry breaking in polar solvents. To investigate how symmetry breaking affects nonlinear optical responses of PDs, an extensive and challenging experimental characterization of a cationic 2-azaazulene polymethine dye, including linear absorption, fluorescence, two-photon absorption and excited-state absorption, has been performed in two solvents with different polarity. Based on this extensive set of experimental data, a three-electronic-state model, accounting for the coupling of electronic degrees of freedom to molecular vibrations and polar solvation, has been reliably parameterized and validated for this dye, fully rationalizing optical spectra in terms of spectral position, intensities and bandshapes. In low-polarity solvents where the dye is mainly in its symmetric form, a nominally forbidden two-photon absorption band is observed, due to a vibronic activation mechanism. Inhomogeneous broadening plays a major role in polar solvents: absorption spectra represent the weighted sum of contributions from states with a variable amount of symmetry breaking, leading to a complex evolution of linear and nonlinear optical spectra with solvent polarity. In more polar solvents, the dominant role of the asymmetric form leads to the activation of two-photon absorption as a result of the symmetry lowering. The subtle interplay between the two mechanisms for two-photon absorption activation, vibronic coupling and polar solvation, can be fully accounted for within the proposed microscopic model allowing a detailed interpretation of the optical spectra of PDs.

  1. Infrared absorption spectra of methylidene radicals in solid neon.

    PubMed

    Lu, Hsiao-Chi; Lo, Jen-Iu; Lin, Meng-Yeh; Peng, Yu-Chain; Chou, Sheng-Lung; Cheng, Bing-Ming; Ogilvie, J F

    2014-07-28

    Infrared absorption lines of methylidene--(12)C(1)H, (13)C(1)H, and (12)C(2)H--dispersed in solid neon at 3 K, recorded after photolysis of methane precursors with vacuum-ultraviolet light at 121.6 nm, serve as signatures of these trapped radicals.

  2. Polarization discrimination fluorescence retrieval from reflectance spectra of algae in seawater: comparison of multicomponent Mie scattering and polarized radiative transfer models with laboratory and field tests

    NASA Astrophysics Data System (ADS)

    Gilerson, A.; Oo, M.; Chowdhary, J.; Gross, B. M.; Moshary, F.; Ahmed, S. A.

    2005-10-01

    Previously, it was shown that it is possible to separate the elastic scattering from the chlorophyll fluorescence signal using a polarization discrimination technique. The separation procedure depends however fundamentally on the degree of polarization of the water leaving radiance. In this paper, we compare polarization effects and efficiency of the fluorescence retrieval by simulating the total and polarized reflectance of waterleaving radiances originating from elastic scattering in case 1 and case 2 waters using radiative transfer and multiple component Mie scattering programs. This is done by superimposing upon these reflectances the contribution of known fluorescence spectra, and by using our polarization discrimination procedure to invert the resulting data back into fluorescence spectra. It is shown that a Mie scattering code which does not take into account multiple scattering effects can strongly overestimate the degree of polarization for case 1 and case 2 waters as well as reflectances in the green part of the spectra. Making use of these results we propose and evaluate an improvement for the traditional height over baseline fluorescence extraction method which strongly overestimates fluorescence value for case 2 waters. For our approach we use inverse absorption spectra of water and chlorophyll a scaled up and fitted to the reflectance spectra in the red and near IR bands with the subsequent retrieval of the fluorescence spectrum and chlorophyll a concentration. Results and potential of this approach are discussed.

  3. Nonnegative matrix factorization: a blind spectra separation method for in vivo fluorescent optical imaging.

    PubMed

    Montcuquet, Anne-Sophie; Hervé, Lionel; Navarro, Fabrice; Dinten, Jean-Marc; Mars, Jérôme I

    2010-01-01

    Fluorescence imaging in diffusive media is an emerging imaging modality for medical applications that uses injected fluorescent markers that bind to specific targets, e.g., carcinoma. The region of interest is illuminated with near-IR light and the emitted back fluorescence is analyzed to localize the fluorescence sources. To investigate a thick medium, as the fluorescence signal decreases with the light travel distance, any disturbing signal, such as biological tissues intrinsic fluorescence (called autofluorescence) is a limiting factor. Several specific markers may also be simultaneously injected to bind to different molecules, and one may want to isolate each specific fluorescent signal from the others. To remove the unwanted fluorescence contributions or separate different specific markers, a spectroscopic approach is explored. The nonnegative matrix factorization (NMF) is the blind positive source separation method we chose. We run an original regularized NMF algorithm we developed on experimental data, and successfully obtain separated in vivo fluorescence spectra.

  4. Data processing of absorption spectra from photoionized plasma experiments at Z

    SciTech Connect

    Hall, I. M.; Durmaz, T.; Mancini, R. C.; Bailey, J. E.; Rochau, G. A.

    2010-10-15

    We discuss the processing of x-ray absorption spectra from photoionized plasma experiments at Z. The data was recorded with an imaging spectrometer equipped with two elliptically bent potassium acid phthalate (KAP) crystals. Both time-integrated and time-resolved data were recorded. In both cases, the goal is to obtain the transmission spectra for quantitative analysis of plasma conditions.

  5. Calculation of polarized IR absorption spectra for trans-1,4-polyisoprenes of various conformations

    NASA Astrophysics Data System (ADS)

    Abdulov, Kh. Sh.

    2008-07-01

    Polarized IR spectra for two conformations of trans-1,4-polyisoprene (α-and β-gutta-percha) were calculated. The IR dichroism of the absorption bands was calculated for both conformations. The computed results for polarized IR spectra and IR dichroism agree reasonably well with the respective experiment data.

  6. The absorption spectra of the complexes of uranium (VI) with some β-diketones

    USGS Publications Warehouse

    Feinstein, H.I.

    1956-01-01

    The absorption spectra of the complexes of uranium (VI) with four β-dike tones were determined under various conditions of pH, concentration of uranium, and alcohol concentration. Under optimum conditions, the maximum molar absorptivity (31,200) is obtained using 2-furoyltrifluoroacetone. This compares with about 4,000 and 19,000 for the thiocyanate and dibenzoylmethane complexes, respectively.

  7. Infrared absorption spectra of human malignant tumor tissues

    NASA Astrophysics Data System (ADS)

    Skornyakov, I. V.; Tolstorozhev, G. B.; Butra, V. A.

    2008-05-01

    We used infrared spectroscopy methods to study the molecular structure of tissues from human organs removed during surgery. The IR spectra of the surgical material from breast, thyroid, and lung are compared with data from histological examination. We show that in malignant neoplasms, a change occurs in the hydrogen bonds of protein macromolecules found in the tissue of the studied organs. We identify the spectral signs of malignant pathology.

  8. Electronic and oscillation absorption spectra of blood plamsa at surgical diseases of thyroid gland

    NASA Astrophysics Data System (ADS)

    Guminetskiy, S. G.; Motrich, A. V.; Poliansky, I. Y.; Hyrla, Ya. V.

    2011-09-01

    The results of investigating the absorption spectra of blood plasma in the visible and infrared parts of spectra obtained using the techniques of spherical photometer and spectrophotometric complex "Specord IR75" are presented. The possibility of using these spectra for diagnoses the cases of diffuse toxic goiter and nodular goiter and control of treatment process in postsurgical period in the cases of thyroid gland surgery is estimated.

  9. Electronic and oscillation absorption spectra of blood plamsa at surgical diseases of thyroid gland

    NASA Astrophysics Data System (ADS)

    Guminetskiy, S. G.; Motrich, A. V.; Poliansky, I. Y.; Hyrla, Ya. V.

    2012-01-01

    The results of investigating the absorption spectra of blood plasma in the visible and infrared parts of spectra obtained using the techniques of spherical photometer and spectrophotometric complex "Specord IR75" are presented. The possibility of using these spectra for diagnoses the cases of diffuse toxic goiter and nodular goiter and control of treatment process in postsurgical period in the cases of thyroid gland surgery is estimated.

  10. Terahertz absorption spectra of oxidized polyethylene and their analysis by quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Komatsu, Marina; Hosobuchi, Masashi; Xie, Xiaojun; Cheng, Yonghong; Furukawa, Yukio; Mizuno, Maya; Fukunaga, Kaori; Ohki, Yoshimichi

    2014-09-01

    Low-density polyethylene, either cross-linked or not, was oxidized and its absorption spectra were measured in the terahertz (THz) range and infrared range. The absorption was increased by the oxidation in the whole THz range. In accord with this, infrared absorption due to carbonyl groups appears. Although these results indicate that the increase in absorption is induced by oxidation, its attribution to resonance or relaxation is unclear. To clarify this point, the vibrational frequencies of three-dimensional polyethylene models with and without carbonyl groups were quantum chemically calculated. As a result, it was clarified that optically inactive skeletal vibrations in polyethylene become active upon oxidation. Furthermore, several absorption peaks due to vibrational resonances are induced by oxidation at wavenumbers from 20 to 100 cm-1. If these absorption peaks are broadened and are superimposed on each other, the absorption spectrum observed experimentally can be reproduced. Therefore, the absorption is ascribable to resonance.

  11. Aerosol-fluorescence spectrum analyzer: real-time measurement of emission spectra of airborne biological particles

    NASA Astrophysics Data System (ADS)

    Hill, Steven C.; Pinnick, Ronald G.; Nachman, Paul; Chen, Gang; Chang, Richard K.; Mayo, Michael W.; Fernandez, Gilbert L.

    1995-10-01

    We have assembled an aerosol-fluorescence spectrum analyzer (AFS), which can measure the fluorescence spectra and elastic scattering of airborne particles as they flow through a laser beam. The aerosols traverse a scattering cell where they are illuminated with intense (50 kW/cm 2) light inside the cavity of an argon-ion laser operating at 488 nm. This AFS can obtain fluorescence spectra of individual dye-doped polystyrene microspheres as small as 0.5 mu m in diameter. The spectra obtained from microspheres doped with pink and green-yellow dyes are clearly different. We have also detected the fluorescence spectra of airborne particles (although not single particles) made from various

  12. FLUORESCENCE CHARACTERIZATION OF IHSS HUMIC SUBSTANCES: TOTAL LUMINESCENCE SPECTRA WITH ABSORBANCE CORRECTION. (R822251)

    EPA Science Inventory

    Total luminescence spectroscopy was applied to the fluorescence characterization of humic substances obtained from the International Humic Substances Society (IHSS). Results show that total luminescence spectra, represented as excitation-emission matrices (EEMs), may be used to d...

  13. Phyllosilicate absorption features in main-belt and outer-belt asteroid reflectance spectra.

    PubMed

    Vilas, F; Gaffey, M J

    1989-11-10

    Absorption features having depths up to 5% are identified in high-quality, high-resolution reflectance spectra of 16 dark asteroids in the main belt and in the Cybele and Hilda groups. Analogs among the CM2 carbonaceous chondrite meteorites exist for some of these asteroids, suggesting that these absorptions are due to iron oxides in phyllosilicates formed on the asteroidal surfaces by aqueous alteration processes. Spectra of ten additional asteroids, located beyond the outer edge of the main belt, show no discernible absorption features, suggesting that aqueous alteration did not always operate at these heliocentric distances.

  14. Kennard-Stepanov relation connecting absorption and emission spectra in an atomic gas.

    PubMed

    Moroshkin, Peter; Weller, Lars; Sass, Anne; Klaers, Jan; Weitz, Martin

    2014-08-01

    The Kennard-Stepanov relation describes a thermodynamic, Boltzmann-type scaling between the absorption and emission spectral profiles of an absorber, which applies in many liquid state dye solutions as well as in semiconductor systems. Here we examine absorption and emission spectra of rubidium atoms in a dense argon buffer gas environment. We demonstrate that the Kennard-Stepanov relation between absorption and emission spectra is well fulfilled in the collisionally broadened atomic gas system. Our experimental findings are supported by a simple theoretical model.

  15. Analysis of laser-induced fluorescence spectra of in vitro plant tissue cultures

    NASA Astrophysics Data System (ADS)

    Muñoz-Muñoz, Ana Celia; Gutiérrez-Pulido, Humberto; Rodríguez-Domínguez, José Manuel; Gutiérrez-Mora, Antonia; Rodríguez-Garay, Benjamín; Cervantes-Martínez, Jesús

    2007-04-01

    We demonstrate the effectiveness of laser-induced fluorescence (LIF) for monitoring the development and stress detection of in vitro tissue cultures in a nondestructive and noninvasive way. The changes in LIF spectra caused by the induction of organogenesis, the increase of the F690/F740 ratio as a result of the stress originated in the organogenic explants due to shoot emergence, and the relationship between fluorescence spectra and shoot development were detected by LIF through closed containers of Saintpaulia ionantha.

  16. Artifacts in Absorption Measurements of Organometal Halide Perovskite Materials: What Are the Real Spectra?

    PubMed

    Tian, Yuxi; Scheblykin, Ivan G

    2015-09-01

    Organometal halide (OMH) perovskites have attracted lots of attention over the last several years due to their very promising performance as the materials for solar cells and light-emitting devices. Photophysical processes in these hybrid organic-inorganic semiconductors are still heavily debated. To know precise absorption spectra is absolutely necessary for quantitative understanding of the fundamental properties of OMH perovskites. We show that to measure the absorption of perovskite materials correctly is a difficult task which could be easily overlooked by the community. Many of the published absorption spectra exhibit a characteristic step-like featureless shape due to light scattering, high optical density of individual perovskite crystals and poor coverage of the substrate. We show how to recognize these artifacts, to avoid them, and to use absorption spectra of films for estimation of the surface coverage ratio. PMID:27120683

  17. Autophaser: an algorithm for automated generation of absorption mode spectra for FT-ICR MS.

    PubMed

    Kilgour, David P A; Wills, Rebecca; Qi, Yulin; O'Connor, Peter B

    2013-04-16

    Phase correction of Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry data allows the spectra to be presented in absorption mode. Absorption mode spectra offer superior mass resolving power (up to a factor of 2), mass accuracy, and sensitivity over the conventional magnitude mode. Hitherto, the use of absorption mode in FT-ICR mass spectrometry has required either specially adapted instrumentation or a manually intensive process of phase correction or has ignored the potentially significant effects of image charge and the associated frequency shifts. Here we present an algorithm that allows spectra recorded on unadapted FT-ICR mass spectrometers to be phase corrected, their baseline deviations removed, and then an absorption mode spectrum presented in an automated manner that requires little user interaction. PMID:23373960

  18. Autophaser: an algorithm for automated generation of absorption mode spectra for FT-ICR MS.

    PubMed

    Kilgour, David P A; Wills, Rebecca; Qi, Yulin; O'Connor, Peter B

    2013-04-16

    Phase correction of Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry data allows the spectra to be presented in absorption mode. Absorption mode spectra offer superior mass resolving power (up to a factor of 2), mass accuracy, and sensitivity over the conventional magnitude mode. Hitherto, the use of absorption mode in FT-ICR mass spectrometry has required either specially adapted instrumentation or a manually intensive process of phase correction or has ignored the potentially significant effects of image charge and the associated frequency shifts. Here we present an algorithm that allows spectra recorded on unadapted FT-ICR mass spectrometers to be phase corrected, their baseline deviations removed, and then an absorption mode spectrum presented in an automated manner that requires little user interaction.

  19. Accurate convergence of transient-absorption spectra using pulsed lasers.

    PubMed

    Brazard, Johanna; Bizimana, Laurie A; Turner, Daniel B

    2015-05-01

    Transient-absorption spectroscopy is a common and well-developed technique for measuring time-dependent optical phenomena. One important aspect, especially for measurements using pulsed lasers, is how to average multiple data acquisition events. Here, we use a mathematical analysis method based on covariance to evaluate various averaging schemes. The analysis reveals that the baseline and the signal converge to incorrect values without balanced detection of the probe, shot-by-shot detection, and a specific method of averaging. Experiments performed with sub-7 fs pulses confirm the analytic results and reveal insights into molecular excited-state vibrational dynamics.

  20. [Application of fluorescence spectra and parallel factor analysis in the classification of edible vegetable oils].

    PubMed

    Wu, Xi-jun; Pan, Zhao; Zhao, Yan-peng; Liu, Hai-long; Zheng, Long-jiang

    2014-08-01

    The fluorescence spectra of 22 samples of 8 kinds of edible vegetable oils (soybean oil, maize oil, olive oil, rice oil, peanut oil, walnut oil, sunflower oil and sesame oil) were measured with FS920 fluorescence spectrometer and the fluorescence matrixs (EEMs) were analyzed with parallel factor (PARAFAC) analysis model. To synthesize the capabilities of material characterization and component identification, fluorescence spectra combined with PARAFAC fulfill the classification of vegetable oils. The map feature (peak position, peak value and peak number) was obtained by analyzing three dimensional spectra and con tour maps in the range of emission wavelength from 260 to 750 nm, and excitation wavelengths from 250 to 550 nm. The fluorescent substances (unsaturated fatty acids, vitamin E and its derivatives, chlorophyll and carotenoid) corresponding to spectrum peaks were determined. The factor-number was selected and the components (vitamin E and its derivatives, linoleic acid and linolenic acid, fatty acid oxidation products, vegetable oil oxidation products) corresponding to each factor were ascertained. The four-factor excitation and emission profiles and projection score plots of PARAFAC model were plotted. Different vegetable oils can be characterized and distinguished with the map features of fluorescence spectra and sample projection plots of PARAFAC model. The results demonstrate the capability of the combination of fluorescence spectra technology and four-factor PARAFAC model for differentiating and characterizing vegetable oils.

  1. Measurements of the Ultraviolet Fluorescence Cross Sections and Spectra of Bacillus Anthracis Simulants

    SciTech Connect

    Stephens, J.R.

    1998-09-01

    Measurements of the ultraviolet autofluorescence spectra and absolute cross sections of the Bacillus anthracis (Ba) simulants Bacillus globigii (Bg), Bacillus megaterium (Bm), Bacillus subtilis (Bs), and Bacillus cereus (Bc) were measured. Fluorescence spectra and cross sections of pine pollen (Pina echinata) were measured for comparison. Both dried vegetative cells and spores separated from the sporulated vegetative material were studied. The spectra were obtained by suspending a small number (<10) of particles in air in our Single Particle Spectroscopy Apparatus (SPSA), illuminating the particles with light from a spectrally filtered arc lamp, and measuring the fluorescence spectra of the particles. The illumination was 280 nm (20 nm FWHM) and the fluorescence spectra was measured between 300 and 450 nm. The fluorescence cross section of vegetative Bg peaks at 320 nm with a maximum cross section of 5 X 10{sup -14} cm{sup 2}/sr-nm-particle while the Bg spore fluorescence peaks at 310 nm with peak fluorescence of 8 X 10{sup -15} cm{sup 2}/sr-nm-particle. Pine pollen particles showed a higher fluorescence peaking at 355 nm with a cross section of 1.7 X 10{sup -13} cm{sup 2}/sr-nm-particle. Integrated cross sections ranged from 3.0 X 10{sup -13} for the Bg spores through 2.25 X 10{sup -12} (cm{sup 2}/sr-particle) for the vegetative cells.

  2. The Infrared Spectra and Absorption Intensities of Amorphous Ices

    NASA Astrophysics Data System (ADS)

    Gerakines, Perry A.; Hudson, Reggie L.; Loeffler, Mark

    2016-06-01

    Our research group is carrying out new IR measurements of icy solids relevant to the outer solar system and to the interstellar medium, with an emphasis on amorphous and crystalline ices below ~ 120 K. Our goal is to update and add to the relatively meager literature on this subject and to provide electronic versions of state-of-the-art data, since the abundances of such molecules cannot be deduced without accurate reference spectra and IR band strengths. In the past year, we have focused on three of the simplest and most abundant components of interstellar and solar-system ices: methane (CH4), carbon dioxide (CO2), and methanol (CH3OH). Infrared spectra from ˜ 4500 to 500 cm-1 have been measured for each of these molecules in μm-thick films at temperatures from 10 to 120 K. All known amorphous and crystalline phases have been reproduced and, for some, presented for the first time. We also report measurements of the index of refraction at 670 nm and the mass densities for each ice phase. Comparisons are made to earlier work where possible. Electronic versions of our new results are available at http://science.gsfc.nasa.gov/691/cosmicice/ constants.html.

  3. The Infrared Spectra and Absorption Intensities of Amorphous Ices

    NASA Astrophysics Data System (ADS)

    Gerakines, Perry A.; Hudson, Reggie L.; Loeffler, Mark

    2016-06-01

    Our research group is carrying out new IR measurements of icy solids relevant to the outer solar system and to the interstellar medium, with an emphasis on amorphous and crystalline ices below ~ 120 K. Our goal is to update and add to the relatively meager literature on this subject and to provide electronic versions of state-of-the-art data, since the abundances of such molecules cannot be deduced without accurate reference spectra and IR band strengths. In the past year, we have focused on three of the simplest and most abundant components of interstellar and solar-system ices: methane (CH4), carbon dioxide (CO2), and methanol (CH3OH). Infrared spectra from ∼ 4500 to 500 cm-1 have been measured for each of these molecules in μm-thick films at temperatures from 10 to 120 K. All known amorphous and crystalline phases have been reproduced and, for some, presented for the first time. We also report measurements of the index of refraction at 670 nm and the mass densities for each ice phase. Comparisons are made to earlier work where possible. Electronic versions of our new results are available at http://science.gsfc.nasa.gov/691/cosmicice/ constants.html.

  4. Monitoring the variability of intrinsic absorption lines in quasar spectra , ,

    SciTech Connect

    Misawa, Toru; Charlton, Jane C.; Eracleous, Michael

    2014-09-01

    We have monitored 12 intrinsic narrow absorption lines (NALs) in five quasars and seven mini-broad absorption lines (mini-BALs) in six quasars for a period of 4-12 yr (1-3.5 yr in the quasar rest-frame). We present the observational data and the conclusions that follow immediately from them, as a prelude to a more detailed analysis. We found clear variability in the equivalent widths (EWs) of the mini-BAL systems but no easily discernible changes in their profiles. We did not detect any variability in the NAL systems or in narrow components that are often located at the center of mini-BAL profiles. Variations in mini-BAL EWs are larger at longer time intervals, reminiscent of the trend seen in variable BALs. If we assume that the observed variations result from changes in the ionization state of the mini-BAL gas, we infer lower limits to the gas density ∼10{sup 3}-10{sup 5} cm{sup –3} and upper limits on the distance of the absorbers from the central engine of the order of a few kiloparsecs. Motivated by the observed variability properties, we suggest that mini-BALs can vary because of fluctuations of the ionizing continuum or changes in partial coverage while NALs can vary primarily because of changes in partial coverage.

  5. Absorption spectra and speciation of plutonium(VI) with phosphate

    SciTech Connect

    Weger, H.T.; Reed, D.

    1996-02-01

    Plutonium(VI)-phosphate species in aqueous solution, at pH < 2.4, formed two species: PuO{sub 2}H{sub 2}PO{sub 4}{sup +} (characterized by an 835 nm absorption band) and the solid phase PuO{sub 2}(H{sub 2}PO{sub 4}){sub 2}. The stability constant {beta} for the PuO{sub 2}H{sub 2}PO{sub 4}{sup +} species was determined to be log {beta} = 2.1 {+-} 0.1 (ionic strength = 0.6--0.9 M) and log {beta}{sup T} = 2.6 {+-} 0.15 (zero ionic strength). Four Pu(VI)-phosphate species (absorption bands at 842, 846, 857, and 866 nm) formed at pH = 2.4 to 12.2 and are characterized by polynuclear behavior, the formation of precipitates, and colloidal properties. The 842 and 846 nm species are believed to be [PuO{sub 2}(HPO{sub 4}){sub m}]{sub n} and [PuO{sub 2}(NaPO{sub 4}){sub m}]{sub n}. The 857 and 866 nm species area as yet unidentified. The speciation of plutonium with phosphate is of interest to radionuclide migration studies because phosphate is present in many groundwaters and may be used as an actinide getter in nuclear waste disposal. An actinide getter is a complexing agent that forms insoluble phases with actinides, thereby reducing their migration.

  6. Chemical Sensitivity of the Sulfur K-Edge X-ray Absorption Spectra of Organic Disulfides.

    PubMed

    Pickering, Ingrid J; Barney, Monica; Cotelesage, Julien J H; Vogt, Linda; Pushie, M Jake; Nissan, Andrew; Prince, Roger C; George, Graham N

    2016-09-22

    Sulfur K-edge X-ray absorption spectroscopy increasingly is used as a tool to provide speciation information about the sulfur chemical form in complex samples, with applications ranging from fossil fuels to soil science to health research. As part of an ongoing program of systematic investigations of the factors that affect the variability of sulfur K near-edge spectra, we have examined the X-ray absorption spectra of a series of organic symmetric disulfide compounds. We have used polarized sulfur K-edge spectra of single crystals of dibenzyl disulfide to confirm the assignments of the major transitions in the spectrum as 1s → (S-S)σ* and 1s → (S-C)σ*. We also have examined the solution spectra of an extended series of disulfides and show that the spectra change in a systematic and predictable manner with the nature of the external group. PMID:27571342

  7. High resolution laser induced fluorescence Doppler velocimetry utilizing saturated absorption spectroscopy

    SciTech Connect

    Aramaki, Mitsutoshi; Ogiwara, Kohei; Etoh, Shuzo; Yoshimura, Shinji; Tanaka, Masayoshi Y.

    2009-05-15

    A high resolution laser induced fluorescence (LIF) system has been developed to measure the flow velocity field of neutral particles in an electron-cyclotron-resonance argon plasma. The flow velocity has been determined by the Doppler shift of the LIF spectrum, which is proportional to the velocity distribution function. Very high accuracy in velocity determination has been achieved by installing a saturated absorption spectroscopy unit into the LIF system, where the absolute value and scale of laser wavelength are determined by using the Lamb dip and the fringes of a Fabry-Perot interferometer. The minimum detectable flow velocity of a newly developed LIF system is {+-}2 m/s, and this performance remains unchanged in a long-time experiment. From the radial measurements of LIF spectra of argon metastable atoms, it is found that there exists an inward flow of neutral particles associated with neutral depletion.

  8. Absorption spectra of shocked liquid CS/sub 2/

    SciTech Connect

    Dallman, J.C.

    1985-01-01

    The importance of shock initiation of high explosives (HE) was understood as early as 1863 when Alfred Nobel introduced the detonator as a means of detonating nitroglycerine. The critical pressure rise times required to achieve shock initiation and steady propagation of detonation are determined by the chemical and mechanical properties of an explosive. Although progress has been made in the understanding of the effects of mechanical properties, the detailed effects of high pressures on chemical reaction mechanisms are still only poorly understood. This paper reports the results of two experiments using CS/sub 2/, which is known to undergo electronic state transitions when shocked to high pressures. The goal of these experiments was to examine the known shock-generated expansion of CS/sub 2/ absorption bands while generating the shocks with a flyer plate system driven by high explosives.

  9. Monitoring the Variability of Intrinsic Absorption Lines in Quasar Spectra

    NASA Astrophysics Data System (ADS)

    Misawa, Toru; Charlton, Jane C.; Eracleous, Michael

    2014-09-01

    We have monitored 12 intrinsic narrow absorption lines (NALs) in five quasars and seven mini-broad absorption lines (mini-BALs) in six quasars for a period of 4-12 yr (1-3.5 yr in the quasar rest-frame). We present the observational data and the conclusions that follow immediately from them, as a prelude to a more detailed analysis. We found clear variability in the equivalent widths (EWs) of the mini-BAL systems but no easily discernible changes in their profiles. We did not detect any variability in the NAL systems or in narrow components that are often located at the center of mini-BAL profiles. Variations in mini-BAL EWs are larger at longer time intervals, reminiscent of the trend seen in variable BALs. If we assume that the observed variations result from changes in the ionization state of the mini-BAL gas, we infer lower limits to the gas density ~103-105 cm-3 and upper limits on the distance of the absorbers from the central engine of the order of a few kiloparsecs. Motivated by the observed variability properties, we suggest that mini-BALs can vary because of fluctuations of the ionizing continuum or changes in partial coverage while NALs can vary primarily because of changes in partial coverage. Based on data collected at Subaru telescope, which is operated by the National Astronomical Observatory of Japan. Based on observations obtained at the European Southern Observatory at La Silla, Chile in programs 65.O-0063(B), 65.O-0474(A), 67.A-0078(A), 68.A-0461(A), 69.A-0204(A), 70.B-0522(A), 072.A-0346(A), 076.A-0860(A), 079.B-0469(A), and 166.A-0106(A).

  10. Simultaneous Fitting of Absorption Spectra and Their Second Derivatives for an Improved Analysis of Protein Infrared Spectra.

    PubMed

    Baldassarre, Maurizio; Li, Chenge; Eremina, Nadejda; Goormaghtigh, Erik; Barth, Andreas

    2015-01-01

    Infrared spectroscopy is a powerful tool in protein science due to its sensitivity to changes in secondary structure or conformation. In order to take advantage of the full power of infrared spectroscopy in structural studies of proteins, complex band contours, such as the amide I band, have to be decomposed into their main component bands, a process referred to as curve fitting. In this paper, we report on an improved curve fitting approach in which absorption spectra and second derivative spectra are fitted simultaneously. Our approach, which we name co-fitting, leads to a more reliable modelling of the experimental data because it uses more spectral information than the standard approach of fitting only the absorption spectrum. It also avoids that the fitting routine becomes trapped in local minima. We have tested the proposed approach using infrared absorption spectra of three mixed α/β proteins with different degrees of spectral overlap in the amide I region: ribonuclease A, pyruvate kinase, and aconitase. PMID:26184143

  11. A method for determining supernatant-free spectra generated from fluorescently stained cells in suspension.

    PubMed

    Plášek, Jaromír; Gášková, Dana

    2014-12-01

    Here we present a fluorometric method for direct determination of supernatant-free fluorescence spectra generated from fluorescently stained cells in suspension. The key element in the new technique is the design of an adapter to a standard cuvette holder that makes it possible to measure front-face fluorescence spectra from thin layers of cells spun down to the bottom of a spectrofluorometric cuvette. We have demonstrated the applicability of this approach and its analytical potential using the suspensions of yeast cells stained with the potentiometric dye of 3,3'-dipropylthiadicarbocyanine, diS-C3(3), and with the specific cell-wall marker calcofluor.

  12. Measurement and feature analysis of absorption spectra of four algal species

    NASA Astrophysics Data System (ADS)

    Zhu, Jianhua; Zhou, Hongli; Han, Bing; Li, Tongji

    2016-04-01

    Two methods for particulate pigments (i.e., quantitative filter technique, QFT, and in vivo measurement, InVivo, respectively) and two methods for dissolved pigments (i.e., Acetone Extracts, AceEx, and high-performance liquid chromatography, HPLC, respectively) were used to obtain the optical absorption coefficient spectra for cultures of four typical algal species. Through normalization and analysis of the spectra, it is shown that (1) the four methods are able to measure optical absorption spectra of particulate and/or dissolved pigments; (2) that the optical absorption spectra of particulate and dissolved pigments were consistent in terms of the peak position in the blue wavelength, and the difference of the peak position in the near infrared wavelength was ~10 nm between each other; and (3) that the leveling effect of the absorption spectra of particulate pigments was significant. These four methods can all effectively measure the absorption coefficients of phytoplankton pigments, while each one has its unique advantages in different applications. Therefore, appropriate method should be carefully selected for various application due to their intrinsic difference.

  13. An experimental study of the electronic absorption and fluorescence spectral properties of new p-substituted-N-phenylpyrroles and their electrosynthesized polymers.

    PubMed

    Diaw, A K D; Gningue-Sall, D; Yassar, A; Brochon, J-C; Henry, E; Aaron, J-J

    2015-01-25

    Electronic absorption and fluorescence spectral properties of new p-substituted-N-phenylpyrroles (N-PhPys), including HOPhPy, MeOPhPy, ThPhPy, PhDPy, DPhDPy, PyPhThThPhPy, and their available, electrosynthesized polymers were investigated. Electronic absorption spectra, fluorescence excitation and emission spectra, fluorescence quantum yields (ΦF) and lifetimes (τF), and other photophysical parameters of these N-PhPy derivatives and their polymers were measured in DMF, DMSO diluted solutions and/or solid state at room temperature. The electronic absorption spectra of N-PhPy derivatives and their polymers included one to several bands, located in the 270-395 nm region, according to the p-phenyl substituent electron-donating effect and conjugated heteroaromatic system length. The fluorescence excitation spectra were characterized by one broad main peak, with, in most cases, one (or more) poorly resolved shoulder (s), appearing in the 270-405 nm region, and their emission spectra were generally constituted of several bands located in the 330-480 nm region. No significant shift of the absorption, fluorescence excitation and emission spectra wavelengths was found upon going from the monomers to the corresponding polymers. ΦF values were high, varying between 0.11 and 0.63, according to the nature of substituents(s) and to the conjugated system extension. Fluorescence decays were mono-exponential for the monomers and poly-exponential for PyPhThThPhPy and for polymers. τF values were relatively short (0.35-5.17 ns), and markedly decreased with the electron-donor character of the phenyl group p-substituent and the conjugated system extension.

  14. Simple Monte Carlo methods to estimate the spectra evaluation error in differential-optical-absorption spectroscopy.

    PubMed

    Hausmann, M; Brandenburger, U; Brauers, T; Dorn, H P

    1999-01-20

    Differential-optical-absorption spectroscopy (DOAS) permits the sensitive measurement of concentrations of trace gases in the atmosphere. DOAS is a technique of well-defined accuracy; however, the calculation of a statistically sound measurement precision is still an unsolved problem. Usually one evaluates DOAS spectra by performing least-squares fits of reference absorption spectra to the measured atmospheric absorption spectra. Inasmuch as the absorbance from atmospheric trace gases is usually very weak, with optical densities in the range from 10(-5) to 10(-3), interference caused by the occurrence of nonreproducible spectral artifacts often determines the detection limit and the measurement precision. These spectral artifacts bias the least-squares fitting result in two respects. First, spectral artifacts to some extent are falsely interpreted as real absorption, and second, spectral artifacts add nonstatistical noise to spectral residuals, which results in a significant misestimation of the least-squares fitting error. We introduce two new approaches to investigate the evaluation errors of DOAS spectra accurately. The first method, residual inspection by cyclic displacement, estimates the effect of false interpretation of the artifact structures. The second method applies a statistical bootstrap algorithm to estimate properly the error of fitting, even in cases when the condition of random and independent scatter of the residual signal is not fulfilled. Evaluation of simulated atmospheric measurement spectra shows that a combination of the results of both methods yields a good estimate of the spectra evaluation error to within an uncertainty of ~10%.

  15. [Discrimination of Red Tide algae by fluorescence spectra and principle component analysis].

    PubMed

    Su, Rong-guo; Hu, Xu-peng; Zhang, Chuan-song; Wang, Xiu-lin

    2007-07-01

    Fluorescence discrimination technology for 11 species of the Red Tide algae at genus level was constructed by principle component analysis and non-negative least squares. Rayleigh and Raman scattering peaks of 3D fluorescence spectra were eliminated by Delaunay triangulation method. According to the results of Fisher linear discrimination, the first principle component score and the second component score of 3D fluorescence spectra were chosen as discriminant feature and the feature base was established. The 11 algae species were tested, and more than 85% samples were accurately determinated, especially for Prorocentrum donghaiense, Skeletonema costatum, Gymnodinium sp., which have frequently brought Red tide in the East China Sea. More than 95% samples were right discriminated. The results showed that the genus discriminant feature of 3D fluorescence spectra of Red Tide algae given by principle component analysis could work well.

  16. Absorption spectra of typical space materials in the vacuum ultraviolet

    NASA Technical Reports Server (NTRS)

    Muscari, J. A.

    1981-01-01

    In order to develop a data base for potential optical degradation of space vacuum ultraviolet instruments, the collected volatile condensed material (CVCM) transmittance was measured in the wavelength region from 115 nm to 300 nm. The parent outgassing materials included: the adhesives, Ablebond 36-2, Trabond BB-2116, EA-9309, and Scotchweld 2216; the paints, Chemglaze Z-306, Z-306 over 9922 primer, Z-306 over AP-131 primer, Cat-A-Lac 463-3-8, 463-3-8 over primer, 3M Nextel 401-C10, and 401-C10 over 901-P1 primer; the resins, Fiberite 934, Solithane 113/C113-300 Formulation no. 1, and 113/C113-300 Formulation no. 8; the lubricants, Lube-Lok 4306 and RT/Duroid 5813; and the double-sided adhesive tape 3M-415. The effect of thermal vacuum conditioning of selected materials was also studied. The transmittance measurements were used to calculate the absorption coefficient for each of 28 different source materials versus wavelength.

  17. New Absorption Spectra of CH_2 Near 780 NM

    NASA Astrophysics Data System (ADS)

    Xin, Ju; Wang, Zhong; Sears, Trevor J.

    2009-06-01

    The near infrared and visible spectrum (tilde{b}^1B_1 - tilde{a}^1A_1) of singlet CH_2 has been the subject of much study. However, the region between the red end of the visible part of the spectrum and about 800 nm has not been recorded since the pioneering work of Herzberg and Johns. We have remeasured the absorption spectrum between approximately 769 and 806 nm at near shot-noise-limited sensitivity and Doppler-limited resolution using a frequency-modulated extended cavity diode laser source. Rotational branches in 7 vibronic bands involving K_a = 0-4 have been assigned using known ground state combination differences. Most of them have not previously been observed and some reassignments of the Herzberg and Johns analysis have been made. Comparison with the most complete available calculated ro-vibronic energy level structure helped considerably in making the assignments, and the observed vibronic levels are assigned to levels of both tilde{a} and tilde{b} electronic character. The calculated energy levels show moderate, up to 10 cm^{-1}, apparently random, differences from the observed levels The new data will certainly help to refine the singlet potential and also provide additional avenues for future kinetics and dynamics studies of the radical. G. Herzberg and J. W. C. Johns Proc. R. Soc. London Ser. A, 295, 107 (1966) J. -P. Gu, G. Hirsch, R J Buenker, M. Brumm, G. Osmann, P. R. Bunker and P. Jensen J. Molec. Struc., 517-8, 247 (2000) Acknowledgments: Work at Brookhaven National Laboratory was carried out under Contract No. DE-AC02-98CH10886 with the U.S. Department of Energy. Ju Xin acknowledges support from the Faculty and Student Teams program of the Educational Programs Department at Brookhaven National Laboratory.

  18. Analyzing LED-induced haemal fluorescent spectra on laboratory small albino rat

    NASA Astrophysics Data System (ADS)

    Gao, Shumei; Luo, Xiaosen; Lan, Xiufeng; Jiao, Fangxiang; Lu, Jian; Ni, Xiaowu; Xu, Jiaying; Lu, Shiyue; Shen, Jian; Liu, Jiangang

    2002-04-01

    Native fluorescence spectral characteristics of red blood cells were studied in the visible region in this paper. Blood samples were collected from normal small albino rats. Native fluorescence spectra of the erythrocyte were induced using Light Emitting Diode (LED) at yellow wavelength about 570+/- 16 nm ((Delta) (lambda) 0.5approximately equals 32nm). As the rat's erythrocyte content of in physiological water is increasing, the fluorescent primary emission peak is red shifted from 588 nm to above 615 nm. Furthermore, the fluorescence intensity at about 600 nm was found to be maximal while the rat's erythrocyte consistence is 1%. Moreover, it is shown in large numbers of experiments that LED-induced fluorescence spectra of the erythrocyte are similar with the whole blood. It may make sense for low- intensity light therapy.

  19. Theoretical studies on absorption, emission, and resonance Raman spectra of Coumarin 343 isomers.

    PubMed

    Wu, Wenpeng; Cao, Zexing; Zhao, Yi

    2012-03-21

    The vibrationally resolved spectral method and quantum chemical calculations are employed to reveal the structural and spectral properties of Coumarin 343 (C343), an ideal candidate for organic dye photosensitizers, in vacuum and solution. The results manifest that the ground-state energies are dominantly determined by different placements of hydrogen atom in carboxylic group of C343 conformations. Compared to those in vacuum, the electronic absorption spectra in methanol solvent show a hyperchromic property together with the redshift and blueshift for the neutral C343 isomers and their deprotonated anions, respectively. From the absorption, emission, and resonance Raman spectra, it is found that the maximal absorption and emission come from low-frequency modes whereas the high-frequency modes have high Raman activities. The detailed spectra are further analyzed for the identification of the conformers and understanding the potential charge transfer mechanism in their photovoltaic applications.

  20. Separation of scattering and absorption contributions in UV/visible spectra of resonant systems.

    PubMed

    Micali, N; Mallamace, F; Castriciano, M; Romeo, A; Scolaro, L M

    2001-10-15

    Resonance light scattering (RLS) is a phenomenon due to an enhancement of the scattered light in close proximity to an absorption band. The effect is easily detectable in the case of strongly absorbing chromophores, which are able to interact, thus leading to large aggregates (Pasternack, R. F.; Collings, P. J. Science 1995, 269, 935). The measurement of absorption spectra from solutions containing such resonant systems can lead to misleading results. In this paper, a simple method is described to obtain absorption spectra of aggregated species with a fairly good correction of the scattering component. The RLS spectrum, obtained using a common spectrofluorimeter, is correlated to the extinction spectrum of the same sample, allowing for an estimation of the scattering contribution to the total extinction spectrum. The method has been successfully applied both on real samples containing aggregated chromophores, such as porphyrins, chlorophyll a and gold colloids, and by simulating extinction spectra.

  1. Laser-excited fluorescence spectra of atomic uranium

    SciTech Connect

    Wang Songyue; Jin Changtai; Shen Mingtao; Wang Xiulan

    1987-05-01

    Using a dc-supply hollow-cathode lamp as a source of uranium vapor and a rhodamine 6G dye laser to excite the vapor optically, it was simple and convenient to detect fluorescence from uranium atoms at 753.393, 763.175, and 763.954 nm. We give a detailed discussion of how we eliminated the intense background emissions, which were principally due to the lamp.

  2. Reassignment of the Iron (3) Absorption Bands in the Spectra of Mars

    NASA Technical Reports Server (NTRS)

    Sherman, D. M.

    1985-01-01

    Absorption features in the near-infrared and visible region reflectance spectra of Mars have been assigned to specific Fe (3+) crystal-field and o(2-) yields Fe(3+) charge transfer transitions. Recently, near-ultraviolet absorption spectra of iron oxides were obtained and the energies of o(2-) yields Fe(3+) charge-transfer (LMCT) transitions were determined from accurate SCF-X # alpha-SW molecular orbital calculations on (FeO6)(9-) and (FeO4)(5-) clusters. Both the theoretical and experimental results, together with existing data in the literature, show that some of the previous Fe(3+) band assignments in the spectra of Mars need to be revised. The theory of Fe(3+) spectra in minerals is discussed and applied to the spectrum of Mars.

  3. THE STRUCTURE OF THE ULTRAVIOLET ABSORPTION SPECTRA OF CERTAIN PROTEINS AND AMINO ACIDS

    PubMed Central

    Coulter, Calvin B.; Stone, Florence M.; Kabat, Elvin A.

    1936-01-01

    1. The absorption spectra of a number of proteins in the region 2500 to 3000 A. have been found to comprise from six to nine narrow bands. In consequence of variation in the relative intensity of these bands from protein to protein, the absorption curve has a characteristic configuration for each protein. 2. These bands correspond closely in position with the narrow bands which appear in the absorption spectra of tryptophan, tyrosin, and phenylalanine. Tryptophan and tyrosin each present three bands, phenylalanine shows nine. 3. The bands in the proteins are accordingly attributed to these amino acids. In the proteins the bands are displaced from the positions which they occupy in the uncombined amino acids, in most instances, by 10 to 35 A. toward longer wavelengths. 4. The absorption spectrum of Pneumococcus Type I antibody resembles that of normal pseudoglobulin but shows characteristic differences. PMID:19872958

  4. Theoretical analysis of electronic absorption spectra of vitamin B12 models

    NASA Astrophysics Data System (ADS)

    Andruniow, Tadeusz; Kozlowski, Pawel M.; Zgierski, Marek Z.

    2001-10-01

    Time-dependent density-functional theory (TD-DFT) is applied to analyze the electronic absorption spectra of vitamin B12. To accomplish this two model systems were considered: CN-[CoIII-corrin]-CN (dicyanocobinamide, DCC) and imidazole-[CoIII-corrin]-CN (cyanocobalamin, ImCC). For both models 30 lowest excited states were calculated together with transition dipole moments. When the results of TD-DFT calculations were directly compared with experiment it was found that the theoretical values systematically overestimate experimental data by approximately 0.5 eV. The uniform adjustment of the calculated transition energies allowed detailed analysis of electronic absorption spectra of vitamin B12 models. All absorption bands in spectral range 2.0-5.0 eV were readily assigned. In particular, TD-DFT calculations were able to explain the origin of the shift of the lowest absorption band caused by replacement of the-CN axial ligand by imidazole.

  5. Low temperature absorption, fluorescence, and hole-burning spectroscopy of photosystem II reaction center complex containing 1 and 2 carotenoides

    NASA Astrophysics Data System (ADS)

    Dědic, R.; Lovčinský, M.; Pšenčík, J.; Vácha, M.; Vácha, F.; Hála, J.

    1999-05-01

    Well defined photosystem II reaction centers from Pisum sativum containing 5 or 6 chlorophyll a (Chl a), 2 pheophytine a (Pheo a), and 1 or 2 β-carotene ( β Car) molecules were prepared by using immobilized metal affinity chromatography. Samples containing 6 Chl a and 1 or 2 β-Car and containing 5 Chl a and 1 β-Car were measured using low temperature absorption, fluorescence and hole-burning spectroscopy. Absorption bands of the β Car (462, 490, and 508 nm) can be clearly distinguished next to the Soret absorption band of Chl a at low temperature. Their relative intensities strongly depend on Chl/Car ratio. The shapes of fluorescence bands are the same for all samples. Persistent spectral holes were burnt into both absorption and fluorescence spectra. This technique provides lifetime of excited state τ1 and Huang-Rhys factor S. Values of τ1 correspond to two picoseconds energy transfer in reaction centers. Huang-Rhys factor S=0.4 appears to be the same for all studied samples.

  6. Experimental determination and interpretation of the fluorescence and fluorescence excitation spectra of chrysene cooled in a supersonic jet

    NASA Astrophysics Data System (ADS)

    Borisevich, N. A.; Dyachenko, G. G.; Petukhov, V. A.; Semenov, M. A.

    2008-12-01

    The fluorescence and fluorescence excitation spectra of jet-cooled chrysene are measured. The frequencies of in-plane vibrations in the ground and first excited singlet electronic states, as well as the relative intensities of transitions between them, are calculated with the MO/M8ST method. Based on these data, experimental spectra are interpreted. In the fluorescence excitation spectrum, the position of the line of the 0-0 transition (28 195 ± 1 cm-1), which is the most intense, is determined. In the experimental fluorescence excitation spectrum, 21 lines correspond to fundamental vibrations (altogether, 37 lines are attributed). This supports our assignment and is consistent with the group-theoretical analysis of vibronic interactions. Upon excitation at the frequency of the 0-0 transition, 10 lines corresponding to the excitation of fundamental vibrations are detected, and all 17 lines observed are attributed. In the fluorescence excitation spectrum, the standard deviation between the calculated and measured frequencies of attributed fundamental vibrations is 19 cm-1, while that in the fluorescence spectrum is 15 cm-1.

  7. Soft X-ray absorption excess in gamma-ray burst afterglow spectra: Absorption by turbulent ISM

    NASA Astrophysics Data System (ADS)

    Tanga, M.; Schady, P.; Gatto, A.; Greiner, J.; Krause, M. G. H.; Diehl, R.; Savaglio, S.; Walch, S.

    2016-10-01

    Two-thirds of long duration gamma-ray bursts (GRBs) show soft X-ray absorption in excess of the Milky Way. The column densities of metals inferred from UV and optical spectra differ from those derived from soft X-ray spectra, at times by an order of magnitude, with the latter being higher. The origin of the soft X-ray absorption excess observed in GRB X-ray afterglow spectra remains a heavily debated issue, which has resulted in numerous investigations on the effect of hot material both internal and external to the GRB host galaxy on our X-ray afterglow observations. Nevertheless, all models proposed so far have either only been able to account for a subset of our observations (i.e. at z> 2), or they have required fairly extreme conditions to be present within the absorbing material. In this paper, we investigate the absorption of the GRB afterglow by a collisionally ionised and turbulent interstellar medium (ISM). We find that a dense (3 cm-3) collisionally ionised ISM could produce UV/optical and soft X-ray absorbing column densities that differ by a factor of 10. However the UV/optical and soft X-ray absorbing column densities for such sightlines are 2-3 orders of magnitude lower in comparison to the GRB afterglow spectra. For those GRBs with a larger soft X-ray excess by up to an order of magnitude, the contribution in absorption from a turbulent ISM as considered here would ease the required conditions of additional absorbing components, such as the GRB circumburst medium and intergalactic medium.

  8. A Novel Acoustic Sensor Approach to Classify Seeds Based on Sound Absorption Spectra

    PubMed Central

    Gasso-Tortajada, Vicent; Ward, Alastair J.; Mansur, Hasib; Brøchner, Torben; Sørensen, Claus G.; Green, Ole

    2010-01-01

    A non-destructive and novel in situ acoustic sensor approach based on the sound absorption spectra was developed for identifying and classifying different seed types. The absorption coefficient spectra were determined by using the impedance tube measurement method. Subsequently, a multivariate statistical analysis, i.e., principal component analysis (PCA), was performed as a way to generate a classification of the seeds based on the soft independent modelling of class analogy (SIMCA) method. The results show that the sound absorption coefficient spectra of different seed types present characteristic patterns which are highly dependent on seed size and shape. In general, seed particle size and sphericity were inversely related with the absorption coefficient. PCA presented reliable grouping capabilities within the diverse seed types, since the 95% of the total spectral variance was described by the first two principal components. Furthermore, the SIMCA classification model based on the absorption spectra achieved optimal results as 100% of the evaluation samples were correctly classified. This study contains the initial structuring of an innovative method that will present new possibilities in agriculture and industry for classifying and determining physical properties of seeds and other materials. PMID:22163455

  9. Leaf Level Chlorophyll Fluorescence Emission Spectra: Narrow Band versus Full 650-800 nm Retrievals

    NASA Astrophysics Data System (ADS)

    Middleton, E.; Zhang, Q.; Campbell, P. K.; Huemmrich, K. F.; Corp, L.; Cheng, Y.

    2012-12-01

    Recently, chlorophyll fluorescence (ChlF) retrievals in narrow spectral regions (< 1 nm, between 750-770 nm) of the near infrared (NIR) region of Earth's reflected radiation have been achieved from satellites, including the Japanese GOSAT and the European Space Agency's Sciamachy/Envisat. However, these retrievals sample the total full-spectrum ChlF and are made at non-optimal wavelengths since they are not located at the peak fluorescence emission features. We wish to estimate the total full-spectrum ChlF based on emissions obtained at selected wavelengths. For this, we drew upon leaf emission spectra measured on corn leaves obtained from a USDA experimental cornfield in MD (USA). These emission spectra were determined for the adaxial and abaxial (i.e., top and underside) surfaces of leaves measured throughout the 2008 and 2011 growing seasons (n>400) using a laboratory instrument (Fluorolog-3, Horiba Scientific, USA), recorded in either 1 nm or 5 nm increments with monochromatic excitation wavelengths of either 532 or 420 nm. The total ChlF signal was computed as the area under the continuous spectral emission curves, summing the emission intensities (counts per second) per waveband. The individual narrow (1 or 5 nm) waveband emission intensities were linearly related to full emission values, with variable success across the spectrum. Equations were developed to estimate total ChlF from these individual wavebands. Here, we report the results for the average adaxial/abaxial emissions. Very strong relationships were achieved for the relatively high fluorescence intensities at the red chlorophyll peak, centered at 685 nm (r2= 0.98, RMSE = 5.53 x 107 photons/s) and in the nearby O2-B atmospheric absorption feature centered at 688 nm (r2 = 0.94, RMSE = 4.04 x 107), as well as in the far-red peak centered at 740 nm (r2=0.94, RMSE = 5.98 x107). Very good retrieval success occurred for the O2-A atmospheric absorption feature on the declining NIR shoulder centered at 760

  10. Infrared absorption spectra of molecular crystals: Possible evidence for small-polaron formation?

    NASA Astrophysics Data System (ADS)

    Pržulj, Željko; Čevizović, Dalibor; Zeković, Slobodan; Ivić, Zoran

    2008-09-01

    The temperature dependence of the position of the so-called anomalous band peaked at 1650cm in the IR-absorption spectrum of crystalline acetanilide (ACN) is theoretically investigated within the small-polaron theory. Its pronounced shift towards the position of the normal band is predicted with the rise of temperature. Interpretation of the IR-absorption spectra in terms of small-polaron model has been critically assessed on the basis of these results.

  11. Fluorescence spectra of blood plasma treated with ultraviolet irradiation in vivo

    NASA Astrophysics Data System (ADS)

    Zalesskaya, G. A.; Maslova, T. O.

    2010-09-01

    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.

  12. Modeling hyperspectral observations of vegetation fluorescence from photosystem level to top-of-atmosphere radiance spectra

    NASA Astrophysics Data System (ADS)

    Verhoef, W.

    2011-12-01

    In support of the candidate ESA mission FLEX, models have been developed to simulate vegetation chlorophyll fluorescence and its observation on the level of single leaves, the canopy and from space. The Fluspect model is based on the PROSPECT leaf model and includes an additional module which calculates the excitation-fluorescence matrix for both sides of the leaf by means of an efficient doubling algorithm. Fluorescence spectra for white incident light, and of course the spectra of reflectance and transmittance, are computed as well. The FluorSAIL model is a numerical variant of SAIL which calculates top-of-canopy fluorescent radiance in the direction of viewing for given incident radiation spectra from the sun and the sky, obtained from the MODTRAN radiative transfer code. In a recent version called FluorSAIL3, high spectral resolution data (0.1 nm) from MODTRAN5 (beta) are used by the model to simulate observations by the candidate FLEX mission. The model computes the directional canopy reflectance with and without fluorescence for the given incident radiation spectra obtained from MODTRAN and the results have been used to evaluate several algorithms for the retrieval of fluorescence from the apparent reflectance signal. In this contribution emphasis will be on the detection of the fluorescence signal, the dependence of fluorescence observations on leaf chlorophyll content and other PROSPECT parameters, canopy structure, and observational conditions, including the properties of the atmosphere. In addition, some attention is paid to the definition of fluorescence quantum efficiencies at photosystem level, leaf level, and canopy level. This is important for the study of the relation between canopy fluorescence and actual photosynthesis. From the simulations it can be concluded that the interpretation of the fluorescence signal is complex, and probably the comparison of actual observations of spectra of fluorescence and reflectance with spectra simulated by a

  13. Spectroscopy of α,ω-dithienyl polyenes: evidence for two-photon absorption states from fluorescence studies

    NASA Astrophysics Data System (ADS)

    Natarajan, Lalgudi V.; Kirkpatrick, Sean M.; Sutherland, Richard L.; Sowards, Laura A.; Spangler, Charles W.; Fleitz, Paul A.; Cooper, Thomas M.

    1998-10-01

    The photophysics of a series (alpha) ,(omega) -dithienyl polyenes was studied. Both one photon excited fluorescence and fluorescence originating from two photon absorption states were investigated. There is strong evidence of two photon absorption from fluorescence studies in agreement with our earlier studies involving nonlinear absorption.

  14. Binding phenomena and fluorescence quenching. II: Photophysics of aromatic residues and dependence of fluorescence spectra on protein conformation

    NASA Astrophysics Data System (ADS)

    Callis, Patrik R.

    2014-12-01

    The three amino acids with aromatic ring side chains-phenylalanine (Phe), tyrosine (Tyr), and especially tryptophan (Trp) have played a long and productive role in helping unlock the secrets of protein behavior by optical spectroscopy (absorption, fluorescence, circular dichroism, etc.) In principle, an appropriately placed Trp will undergo fluorescence wavelength and/or intensity changes upon whatever functional process a protein performs. Although perceived to be enigmatic and not well understood, Trp is arguably now better understood than many of the extrinsic probes currently in use. Basic principles of intrinsic tryptophan fluorescence quenching and wavelength shifts in proteins are presented, with strong emphasis on the importance of electrostatics. The condensed description of findings from recent experiments and simulations of tryptophan fluorescence and intrinsic quenching in proteins is designed to help authors in planning and interpreting experimental results of ligand binding studies.

  15. Search for CO absorption bands in IUE far-ultraviolet spectra of cool stars

    NASA Technical Reports Server (NTRS)

    Gessner, Susan E.; Carpenter, Kenneth G.; Robinson, Richard D.

    1994-01-01

    Observations of the red supergiant (M2 Iab) alpha Ori with the Goddard High Resolution Spectrograph (GHRS) on board the Hubble Space Telescope (HST) have provided an unambiguous detection of a far-ultraviolet (far-UV) chromospheric continuum on which are superposed strong molecular absorption bands. The absorption bands have been identified by Carpenter et al. (1994) with the fourth-positive A-X system of CO and are likely formed in the circumstellar shell. Comparison of these GHRS data with archival International Ultraviolet Explorer (IUE) spectra of alpha Ori indicates that both the continuum and the CO absorption features can be seen with IUE, especially if multiple IUE spectra, reduced with the post-1981 IUESIPS extraction procedure (i.e., with an oversampling slit), are carefully coadded to increase the signal to noise over that obtainable with a single spectrum. We therefore initiated a program, utilizing both new and archival IUE Short Wavelength Prime (SWP) spectra, to survey 15 cool, low-gravity stars, including alpha Ori, for the presence of these two new chromospheric and circumstellar shell diagnostics. We establish positive detections of far-UV stellar continua, well above estimated IUE in-order scattered light levels, in spectra of all of the program stars. However, well-defined CO absorption features are seen only in the alpha Ori spectra, even though spectra of most of the program stars have sufficient signal to noise to allow the dectection of features of comparable magnitude to the absorptions seen in alpha Ori. Clearly if CO is present in the circumstellar environments of any of these stars, it is at much lower column densities.

  16. Absorption spectra of wide-gap semiconductors in their transparency region

    NASA Astrophysics Data System (ADS)

    Imangholi, Babak; Hasselbeck, Michael P.; Sheik-Bahae, Mansoor

    2003-11-01

    The linear absorption spectra of GaP, TiO 2, ZnSe, and ZnS are measured in their transparency range using a two-color, excite-probe Z-scan. ZnS has the lowest absorption coefficient (˜10 -5 cm -1) in the wavelength range 840-900 nm, making it an excellent material for use as a luminescence extracting lens in semiconductor laser cooling experiments. Direct observation of two-photon absorption in ZnSe using only low power, continuous laser beams is also reported.

  17. Correction method for the self-absorption effects in fluorescence extended X-ray absorption fine structure on multilayer samples.

    PubMed

    Li, Wen Bin; Yang, Xiao Yue; Zhu, Jing Tao; Tu, Yu Chun; Mu, Bao Zhong; Yu, Hai Sheng; Wei, Xiang Jun; Huang, Yu Ying; Wang, Zhan Shan

    2014-05-01

    A novel correction method for self-absorption effects is proposed for extended X-ray absorption fine structure (EXAFS) detected in the fluorescence mode on multilayer samples. The effects of refraction and multiple reflection at the interfaces are fully considered in this correction method. The correction is performed in k-space before any further data analysis, and it can be applied to single-layer or multilayer samples with flat surfaces and without thickness limit when the model parameters for the samples are known. The validity of this method is verified by the fluorescence EXAFS data collected for a Cr/C multilayer sample measured at different experimental geometries. PMID:24763646

  18. Evidence from action and fluorescence spectra that UV-induced violet-blue-green fluorescence enhances leaf photosynthesis.

    PubMed

    Mantha, S V; Johnson, G A; Day, T A

    2001-03-01

    We assessed the contribution of UV-induced violet-blue-green leaf fluorescence to photosynthesis in Poa annua, Sorghum halepense and Nerium oleander by measuring UV-induced fluorescence spectra (280-380 nm excitation, 400-550 nm emission) from leaf surfaces and determining the monochromatic UV action spectra for leaf photosynthetic O2-evolution. Peak fluorescence emission wavelengths from leaf surfaces ranged from violet (408 nm) to blue (448 nm), while excitation peaks for these maxima ranged from 333 to 344 nm. Action spectra were developed by supplementing monochromatic radiation from 280 to 440 nm, in 20 nm increments, to a visible nonsaturating background of 500 mumol m-2 s-1 photosynthetically active radiation and measuring photosynthetic O2-evolution rates. Photosynthetic rates tended to be higher with the 340 nm supplement than with higher or lower wavelength UV supplements. Comparing photosynthetic rates with the 340 nm supplement to those with the 400 nm supplement, the percentage enhancement in photosynthetic rates at 340 nm ranged from 7.8 to 9.8%. We suspect that 340 nm UV improves photosynthetic rates via fluorescence that provides violet-blue-green photons for photosynthetic energy conversion because (1) the peak excitation wavelength (340 nm) for violet-blue-green fluorescence from leaves was also the most effective UV wavelength at enhancing photosynthetic rates, and (2) the magnitude of photosynthetic enhancements attributable to supplemental 340 nm UV was well correlated (R2 = 0.90) with the apparent intensity of 340 nm UV-induced violet-blue-green fluorescence emission from leaves.

  19. Absorption Band Modeling in Reflectance Spectra: Availability of the Modified Gaussian Model

    NASA Astrophysics Data System (ADS)

    Sunshine, J. M.; Pieters, C. M.; Pratt, S. F.; McNaron-Brown, K. S.

    1999-03-01

    The modified Gaussian model, a physically based description of absorption bands in spectra, has been updated to provide compatibility with most computer systems. These new versions, written in MATLAB and IDL, are available at the RELAB Website (www.planetary.brown.edu).

  20. Oxygen K-edge absorption spectra of small molecules in the gas phase

    SciTech Connect

    Yang, B.X.; Kirz, J.; Sham, T.K.

    1986-01-01

    The absorption spectra of O/sub 2/, CO, CO/sub 2/ and OCS have been recorded in a transmission mode in the energy region from 500 to 950 eV. Recent observation of EXAFS in these molecules is confirmed in this study. 7 refs., 3 figs.

  1. Principal-components analysis of fluorescence cross-section spectra from pathogenic and simulant bacteria

    NASA Astrophysics Data System (ADS)

    Heaton, Harold I.

    2005-10-01

    Principal-components analysis of a new set of highly resolved (<1 nm) fluorescence cross-section spectra excited at 354.7 nm over the 370 646 nm band has been used to demonstrate the potential ability of UV standoff lidars to discriminate among particular biological warfare agents and simulants over short ranges. The remapped spectra produced by this technique from Bacillus globigii (Bg) and Bacillus anthracis (Ba) spores were sufficiently different to allow them to be cleanly separated, and the Ba spectra obtained from Sterne and Ames strain spores were distinguishable. These patterns persisted as the spectral resolution was subsequently degraded in processing from ˜1 to 34 nm. This is to the author's knowledge the first time that resolved fluorescence spectra from biological warfare agents have been speciated or shown to be distinguishably different from those normally used surrogates by optical spectroscopy.

  2. Analysis of laser-induced fluorescence spectra of in vitro plant tissue cultures.

    PubMed

    Muñoz-Muñoz, Ana Celia; Gutiérrez-Pulido, Humberto; Rodríguez-Domínguez, José Manuel; Gutiérrez-Mora, Antonia; Rodríguez-Garay, Benjamín; Cervantes-Martínez, Jesús

    2007-04-10

    We demonstrate the effectiveness of laser-induced fluorescence (LIF) for monitoring the development and stress detection of in vitro tissue cultures in a nondestructive and noninvasive way. The changes in LIF spectra caused by the induction of organogenesis, the increase of the F690/F740 ratio as a result of the stress originated in the organogenic explants due to shoot emergence, and the relationship between fluorescence spectra and shoot development were detected by LIF through closed containers of Saintpaulia ionantha. PMID:17384731

  3. A Parallel Reconstruction Scheme in Fluorescence Tomography Based on Contrast of Independent Inversed Absorption Properties

    PubMed Central

    Yi, Ji; Bai, Jing

    2006-01-01

    Based on an independent forward model in fluorescent tomography, a parallel reconstructed scheme for inhomogeneous mediums with unknown absorption property is proposed in this paper. The method considers the two diffusion equations as separately describing the propagation of excited light in tissues with and without fluorescent probes inside. Then the concentration of fluorophores is obtained directly through the difference between two estimations of absorption coefficient which can be parallel inversed. In this way, the multiparameter estimation problem in fluorescent tomography is transformed into two independent single-coefficient determined schemes of diffusion optical tomography (DOT). Any algorithms proved to be efficient and effective in DOT can be directly applied here. In this study the absorption property is estimated from the independent diffusion equations by a gradient-based optimization method with finite element method (FEM) solving the forward model. Simulation results of three representative occasions show that the reconstructed method can well estimate fluorescent property and tissue absorption distribution. PMID:23165045

  4. Electronically excited dipole moment of 4-aminobenzonitrile from thermochromic absorption and fluorescence measurements

    NASA Astrophysics Data System (ADS)

    Kawski, A.; Kukliński, B.; Bojarski, P.

    2006-07-01

    The effect of temperature on absorption and fluorescence spectra of 4-aminobenzonitrile (ABN) in 1,2-dichloroethane is studied for temperature ranging from 296 K to 343 K. The analysis of absorption and fluorescence band shift on the basis of Bilot and Kawski theory [L. Bilot, A. Kawski, Z. Naturforsch. 17a (1962) 621], for the known dipole moment in the ground state μg = 5.92 D, and α/ a3 = 0.5 ( α is the polarizability and a is the Onsager interaction radius of the solute) yields for ABN: (1) the empirical Onsager interaction radius a = 3.3 Å, (2) the dipole moment in the excited S 1 state μe = 7.14 D which agrees very well with the value of μe = 7.20 D obtained by Borst et al. [D.R. Borst, T.M. Korter, D.W. Pratt, Chem. Phys. Lett. 350 (2001) 485] from Stark effect studies. Both values of μe concern free ABN molecule and differ significantly from the values of μg (8.0 D, 8.5 D and 8.3 D in cyclohexane, benzene and 1,4-dioxane, respectively) obtained by Schuddeboom et al. [W. Schuddeboom, S.A. Jonker, J.M. Warman, U. Leinhos, W. Kühnle, K.A. Zachariasse, J. Phys. Chem. 96 (1992) 10809] from the time-resolved microwave conductivity measurements which are solvent-dependent. The group moment additivity law in the case of ABN molecule is approximately applicable, both in the ground and in the excited electronic state.

  5. Calibration and analysis of spatially resolved x-ray absorption spectra from a nonuniform plasma

    SciTech Connect

    Knapp, P. F.; Hansen, S. B.; Pikuz, S. A.; Shelkovenko, T. A.; Hammer, D. A.

    2012-07-15

    We report here the calibration and analysis techniques used to obtain spatially resolved density and temperature measurements of a pair of imploding aluminum wires from x-ray absorption spectra. A step wedge is used to measure backlighter fluence at the film, allowing transmission through the sample to be measured with an accuracy of {+-}14% or better. A genetic algorithm is used to search the allowed plasma parameter space and fit synthetic spectra with 20 {mu}m spatial resolution to the measured spectra, taking into account that the object plasma nonuniformity must be physically reasonable. The inferred plasma conditions must be allowed to vary along the absorption path in order to obtain a fit to the spectral data. The temperature is estimated to be accurate to within {+-}25% and the density to within a factor of two. This information is used to construct two-dimensional maps of the density and temperature of the object plasma.

  6. Local environment of metal ions in phthalocyanines: K-edge X-ray absorption spectra.

    PubMed

    Rossi, G; d'Acapito, F; Amidani, L; Boscherini, F; Pedio, M

    2016-09-14

    We report a detailed study of the K-edge X-ray absorption spectra of four transition metal phthalocyanines (MPc, M = Fe, Co, Cu and Zn). We identify the important single and multiple scattering contributions to the spectra in the extended energy range and provide a robust treatment of thermal damping; thus, a generally applicable model for the interpretation of X-ray absorption fine structure spectra is proposed. Consistent variations of bond lengths and Debye Waller factors are found as a function of atomic number of the metal ion, indicating a variation of the metal-ligand bond strength which correlates with the spatial arrangement and occupation of molecular orbitals. We also provide an interpretation of the near edge spectral features in the framework of a full potential real space multiple scattering approach and provide a connection to the local electronic structure. PMID:27510989

  7. Calculation of Electronic Absorption Spectra with Account of Thermal Geometry Fluctuations

    NASA Astrophysics Data System (ADS)

    Guzha, Maris V.; Svitenkov, Andrew I.

    2016-08-01

    An influence of thermal fluctuations of molecule's geometry on calculated electronic-absorption Vis/Uv spectra is considered. Paper presents the quantum chemical modeling of the electronic-absorption spectra for the collection of graphene samples (44, 56, 60, 68 atoms). The calculations were performed by time dependent density functional theory (TDDFT) method in combination with molecular dynamics (MD) simulation at T=300 K. The noticeable changing of spectra relative to single point TDDFT calculation was discovered for two of four structures. We associate achieved results with perturbation of hydrogen and carbon atoms on the edges of the structures. We believe that suggested methodology will be useful in application engineering researches of novel molecules and molecular complexes.

  8. Local environment of metal ions in phthalocyanines: K-edge X-ray absorption spectra.

    PubMed

    Rossi, G; d'Acapito, F; Amidani, L; Boscherini, F; Pedio, M

    2016-09-14

    We report a detailed study of the K-edge X-ray absorption spectra of four transition metal phthalocyanines (MPc, M = Fe, Co, Cu and Zn). We identify the important single and multiple scattering contributions to the spectra in the extended energy range and provide a robust treatment of thermal damping; thus, a generally applicable model for the interpretation of X-ray absorption fine structure spectra is proposed. Consistent variations of bond lengths and Debye Waller factors are found as a function of atomic number of the metal ion, indicating a variation of the metal-ligand bond strength which correlates with the spatial arrangement and occupation of molecular orbitals. We also provide an interpretation of the near edge spectral features in the framework of a full potential real space multiple scattering approach and provide a connection to the local electronic structure.

  9. Site-selective excitation and polarized absorption and emission spectra of trivalent thulium and erbium in strontium fluorapatite

    NASA Astrophysics Data System (ADS)

    Gruber, John B.; Wright, Andrew O.; Seltzer, Michael D.; Zandi, Bahram; Merkle, Larry D.; Hutchinson, J. Andrew; Morrison, Clyde A.; Allik, Toomas H.; Chai, Bruce H. T.

    1997-05-01

    Polarized fluorescence spectra produced by site-selective excitation, and conventional polarized absorption spectra were obtained for Tm3+ and Er3+ ions individually incorporated into single crystals of strontium fluorapatite, Sr5(PO4)3F, also known as SFAP. Substitution of the trivalent rare earth ion for divalent strontium was achieved by passive charge compensation during Czochralski growth of the fluorapatite crystals. Spectra were obtained between 1780 and 345 nm at temperatures from 4 K to room temperature on crystals having the hexagonal structure [P63/m(C6h2)]. The polarized fluorescence spectra due to transitions from multiplet manifolds of Tm3+(4f12), including 1D2, 1G4, and 3H4 to manifolds 3H6 (the ground-state manifold), 3F4, 3H5, 3H4, and 3F3 were analyzed for the details of the crystal-field splitting of the manifolds. Fluorescence lifetimes were measured for Tm3+ transitions from 1D2, 1G4, and 3H4 at room temperature and from 1G4 at 16 K. Results of the analysis indicate that the majority of Tm3+ ions occupy sites having Cs symmetry. A point-charge lattice-sum calculation was made in which the crystal-field components, Anm, were determined assuming that trivalent thulium replaces divalent strontium in the metal site having Cs symmetry. Results support the conclusion that the nearest-neighbor fluoride (F-) is replaced by divalent oxygen (O2-), thus preserving overall charge neutrality and local symmetry. Crystal-field splitting calculations predict energy levels in agreement with results obtained from an analysis of the experimental data. By varying the crystal-field parameters, Bnm, we obtained a rms difference of 7 cm-1 between 43 calculated and experimental Stark levels for Tm3+(4f12) in Tm:SFAP. Absorption and fluorescence spectra are also reported for Er3+ ions in Er:SFAP. Measurement of the temporal decay of the room temperature fluorescence from the 4I11/2 and 4I13/2 manifolds yielded fluorescence lifetimes of 230±20 μs and 8.9±0.1 ms

  10. Possible spinel absorption bands in S-asteroid visible reflectance spectra

    NASA Technical Reports Server (NTRS)

    Hiroi, T.; Vilas, F.; Sunshine, J. M.

    1994-01-01

    Minor absorption bands in the 0.55 to 0.7 micron wavelength range of reflectance spectra of 10 S asteroids have been found and compared with those of spinel-group minerals using the modified Gaussian model. Most of these S asteroids are consistently shown to have two absorption bands around 0.6 and 0.67 micron. Of the spinel-group minerals examined in this study, the 0.6 and 0.67 micron bands are most consistent with those seen in chromite. Recently, the existence of spinels has also been detected from the absorption-band features around 1 and 2 micron of two S-asteroid reflectance spectra, and chromite has been found in a primitive achondrite as its major phase. These new findings suggest a possible common existence of spinel-group minerals in the solar system.

  11. Radiatively driven winds for different power law spectra. [for explaining narrow and broad quasar absorption lines

    NASA Technical Reports Server (NTRS)

    Beltrametti, M.

    1980-01-01

    The analytic solutions for radiatively driven winds are given for the case in which the winds are driven by absorption of line and continuum radiation. The wind solutions are analytically estimated for different parameters of the central source and for different power law spectra. For flat spectra, three sonic points can exist; it is shown, however, that only one of these sonic points is physically realistic. Parameters of the central source are given which generate winds of further interest for explaining the narrow and broad absorption lines in quasars. For the quasar model presented here, winds which could give rise to the narrow absorption lines are generated by central sources with parameters which are not realistic for quasars.

  12. Absorption spectra of PTCDI: A combined UV-Vis and TD-DFT study

    NASA Astrophysics Data System (ADS)

    Oltean, Mircea; Calborean, Adrian; Mile, George; Vidrighin, Mihai; Iosin, Monica; Leopold, Loredana; Maniu, Dana; Leopold, Nicolae; Chiş, Vasile

    2012-11-01

    Absorption spectra of PTCDI (3,4,9,10-perylene-tetracarboxylic-diimide) have been investigated in chloroform, N,N'-dimethylformamide (DMF) and dimethylsulfoxide (DMSO). While no signature of assembled PTCDI molecules is observed in chloroform solution, distinct bands assigned to their aggregation have been identified in DMF and DMSO solutions. PTCDI monomers show very similar absorption patterns in chloroform and DMSO solutions. Experimental data, including the vibronic structure of the absorption spectra were explained based on the Franck-Condon approximation and quantum chemical results obtained at PBE0-DCP/6-31+G(d,p) level of theory. Geometry optimization of the first excited state leads to a nice agreement between the calculated adiabatic transition energies and experimental data.

  13. Exploring protein solution structure: Second moments of fluorescent spectra report heterogeneity of tryptophan rotamers.

    PubMed

    Gasymov, Oktay K; Abduragimov, Adil R; Glasgow, Ben J

    2015-01-01

    Trp fluorescent spectra appear as a log-normal function but are usually analyzed with λmax, full width at half maximum, and the first moment of incomplete spectra. Log-normal analyses have successfully separated fluorescence contributions from some multi-Trp proteins but deviations were observed in single Trp proteins. The possibility that disparate rotamer environments might account for these deviations was explored by moment spectral analysis of single Trp mutants spanning the sequence of tear lipocalin as a model. The analysis required full width Trp spectra. Composite spectra were constructed using log-normal analysis to derive the inaccessible blue edge, and the experimentally obtained spectra for the remainder. First moments of the composite spectra reflected the site-resolved secondary structure. Second moments were most sensitive for spectral deviations. A novel parameter, derived from the difference of the second moments of composite and simulated log-normal spectra correlated with known multiple heterogeneous rotamer conformations. Buried and restricted side chains showed the most heterogeneity. Analyses applied to other proteins further validated the method. The rotamer heterogeneity values could be rationalized by known conformational properties of Trp residues and the distribution of nearby charged groups according to the internal Stark effect. Spectral heterogeneity fits the rotamer model but does not preclude other contributing factors. Spectral moment analysis of full width Trp emission spectra is accessible to most laboratories. The calculations are informative of protein structure and can be adapted to study dynamic processes. PMID:26119357

  14. Selective nonspecific solvation under dielectric saturation and fluorescence spectra of dye solutions in binary solvents.

    PubMed

    Bakhshiev, N G; Kiselev, M B

    1991-09-01

    The influence of selective nonspecific solvation on the fluorescence spectra of three substitutedN-methylphthalimides in a binary solvent system consisting of a nonpolar (n-heptane) and a polar (pyridine) component has been studied under conditions close to dielectric saturation. The substantially nonlinearity of the effect is confirmation that the spectral shifts of fluorescence bands depend on the number of polar solvent molecules involved in solvating the dye molecule. The measured fluorescence spectral shifts determined by substituting one nonpolar solvent molecula with a polar one in the proximity of the dye molecule agree quantitatively with the forecasts of the previously proposed semiempirical theory which describes this nonlinear solvation phenomenon.

  15. Time-resolved spectroscopic fluorescence imaging, transient absorption and vibrational spectroscopy of intact and photo-inhibited photosynthetic tissue.

    PubMed

    Lukins, Philip B; Rehman, Shakil; Stevens, Gregory B; George, Doaa

    2005-01-01

    Fluorescence, absorption and vibrational spectroscopic techniques were used to study spinach at the photosystem II (PS II), chloroplast and cellular levels and to determine the effects and mechanisms of ultraviolet-B (UV-B) photoinhibition of these structures. Two-photon fluorescence spectroscopic imaging of intact chloroplasts shows significant spatial variations in the component fluorescence spectra in the range 640-740 nm, indicating that the type and distribution of chlorophylls vary markedly with position in the chloroplast. The chlorophyll distributions and excitonic behaviour in chloroplasts and whole plant tissue were studied using picosecond time-gated fluorescence imaging, which also showed UV-induced kinetic changes that clearly indicate that UV-B induces both structural and excitonic uncoupling of chlorophylls within the light-harvesting complexes. Transient absorption measurements and low-frequency infrared and Raman spectroscopy show that the predominant sites of UV-B damage in PS II are at the oxygen-evolving centre (OEC) itself, as well as at specific locations near the OEC-binding sites.

  16. Plasmon-induced modulation of the emission spectra of the fluorescent molecules near gold nanorods.

    PubMed

    Zhao, Lei; Ming, Tian; Chen, Huanjun; Liang, Yao; Wang, Jianfang

    2011-09-01

    Both the excitation and emission processes of a fluorescent molecule positioned near a noble metal nanocrystal can interact strongly with the localized surface plasmon resonance of the metal nanocrystal. While the effects of this plasmon-fluorophore interaction on the intensity, polarization, and direction of the fluorescence emission have been intensively investigated, the plasmonic effect on the emission spectrum has barely been explored. We show, on the single-particle level, that the localized surface plasmon resonance of Au nanorods can strongly alter the spectral profile of the emission from adjacent fluorescent molecules. The fluorescent molecules are embedded in a mesostructured silica shell that is uniformly coated on each Au nanorod. The longitudinal plasmon resonance wavelengths of the nanorods are deliberately shifted away from the intrinsic fluorescence emission peak wavelength by synthetically tuning the nanorod aspect ratio. The resultant emission spectra of the fluorescent molecules are found to be remarkably modulated. Besides the intrinsic fluorescence peak, a plasmon-induced new peak emerges at the plasmon resonance wavelength. The intensity of this plasmon-induced fluorescence peak increases as the size of the Au nanorod is increased. This spectral modulation can be understood by depicting the decay process of the fluorophore with multiple vibrational energy levels. The plasmon with a specific resonance energy will enhance the transition rate between the energy levels that have the transition energy approximately equal to the plasmon energy. This plasmon-enhanced transition rate results in a modulated spectral profile of the fluorescence emission.

  17. Temperature and pH effects on myoglobin optical absorption spectra

    NASA Astrophysics Data System (ADS)

    Ciesielski, Wayne A.; Arakaki, Lorilee S. L.; Schenkman, Kenneth A.

    2005-03-01

    Myoglobin is an important intracellular oxygen transport molecule in muscle. Oxygen binding to myoglobin can be determined spectroscopically due to differences in absorption of oxymyoglobin and deoxymyoglobin. Myoglobin oxygenation can be used as a measure of intracellular oxygen tension in muscle. We sought to determine the effects of differences in temperature and pH on myoglobin absorption spectra in the near-infrared spectral region. Transmission spectra were taken of pure solutions of oxymyoglobin and deoxymyoglobin at 10°, 20°, 30°, and 40°C at pH values of 6.0, 7.0, and 8.0 (n=4). In second derivative spectra at 40°C, the deoxymyoglobin peak near 760 nm was shifted by 0.9-1.2 nm toward longer wavelengths relative to 10°C at constant pH. Differences in pH did not result in statistically significant shifts in this peak at constant temperature. Estimations of myoglobin saturation from myoglobin spectra with intermediate saturations were obtained by least squares (LS) and partial least squares (PLS) analyses. Both algorithms estimate myoglobin saturation with small root mean square errors (<1e-6) when component spectra and calibration set spectra are at the same temperature as test spectra (n=100). However, when spectra at 20°C or 40°C were used as component spectra in LS with test spectra at 30°C (all at pH 7.0), errors were 0.8% and 1.4%, respectively. PLS analysis of 30°C test spectra using 20°C or 40°C calibration set spectra yielded errors of 1.6% and 1.5%, respectively. When the PLS analysis is endpoint corrected, these errors become vanishingly small. These results demonstrate that peak shifts due to temperature are potential sources of error if calibration and test spectra differ by 10°C. These errors can be minimized by appropriate spectral analytic methods.

  18. Modeling absorption spectra for detection of the combustion products of jet engines by laser remote sensing.

    PubMed

    Voitsekhovskaya, Olga K; Kashirskii, Danila E; Egorov, Oleg V; Shefer, Olga V

    2016-05-10

    The absorption spectra of exhaust gases (H2O, CO, CO2, NO, NO2, and SO2) and aerosol (soot and Al2O3) particles were modeled at different temperatures for the first time and suitable spectral ranges were determined for conducting laser remote sensing of the combustion products of jet engines. The calculations were conducted on the basis of experimental concentrations of the substances and the sizes of the aerosol particles. The temperature and geometric parameters of jet engine exhausts were also taken from the literature. The absorption spectra were obtained via the line-by-line method, making use of the spectral line parameters from the authors' own high-temperature databases (for NO2 and SO2 gases) and the HITEMP 2010 database, and taking into account atmospheric transmission. Finally, the theoretical absorption spectra of the exhaust gases were plotted at temperatures of 400, 700, and 1000 K, and the impact of aerosol particles on the total exhaust spectra was estimated in spectral ranges suitable for remote sensing applications. PMID:27168298

  19. THERMAL ABSORPTION AS THE CAUSE OF GIGAHERTZ-PEAKED SPECTRA IN PULSARS AND MAGNETARS

    SciTech Connect

    Lewandowski, Wojciech; Rożko, Karolina; Kijak, Jarosław; Melikidze, George I.

    2015-07-20

    We present a model that explains the observed deviation of the spectra of some pulsars and magnetars from the power-law spectra that are seen in the bulk of the pulsar population. Our model is based on the assumption that the observed variety of pulsar spectra can be naturally explained by the thermal free–free absorption that takes place in the surroundings of the pulsars. In this context, the variety of the pulsar spectra can be explained according to the shape, density, and temperature of the absorbing media and the optical path of the line of sight across it. We have put specific emphasis on the case of the radio magnetar SGR J1745–2900 (also known as the Sgr A* magnetar), modeling the rapid variations of the pulsar spectrum after the outburst of 2013 April as due to the free–free absorption of the radio emission in the electron material ejected during the magnetar outburst. The ejecta expands with time and consequently the absorption rate decreases and the shape of the spectrum changes in such a way that the peak frequency shifts toward the lower radio frequencies. In the hypothesis of an absorbing medium, we also discuss the similarity between the spectral behavior of the binary pulsar B1259–63 and the spectral peculiarities of isolated pulsars.

  20. C IV Broad Absorption Line Variability in QSO spectra from SDSS I-III Surveys

    NASA Astrophysics Data System (ADS)

    De Cicco, D.; Brandt, W. N.; Paolillo, M.; Grier, C. J.

    2016-08-01

    We present the results of our study of C IV broad absorption line (BAL) variability in the spectra of more than 1500 QSO's from several SDSS I-III surveys. Absorption lines in QSO spectra are due to outflowing winds which originate from the accretion disk, at a distance on the order of 1/100 - 1/10 pc from the central super-massive black hole (SMBH). Winds trigger the accretion mechanism onto the SMBH removing angular momentum from the disk and, since they evacuate gas from the host galaxy, they are believed to play a fundamental role in galaxy evolution. Absorption lines can be classified on the basis of their width and of the observed transitions, and their equivalent width can change on timescales from months to years, due to variations in the covering factor and/or in the ionization level. We analyzed the largest sample ever used for such kind of studies. We find that the fraction of disappearing BALs is three times larger than the one found in previous works. Strong evidence is found for a coordinated variability in spectra with multiple BAL troughs which may be interpreted in terms of disk-wind rotation, and/or variations in the physical status of the shielding gas. We also find that, in spectra with multiple BAL troughs, the disappearing ones are generally those with the highest central velocity.

  1. Modeling absorption spectra for detection of the combustion products of jet engines by laser remote sensing.

    PubMed

    Voitsekhovskaya, Olga K; Kashirskii, Danila E; Egorov, Oleg V; Shefer, Olga V

    2016-05-10

    The absorption spectra of exhaust gases (H2O, CO, CO2, NO, NO2, and SO2) and aerosol (soot and Al2O3) particles were modeled at different temperatures for the first time and suitable spectral ranges were determined for conducting laser remote sensing of the combustion products of jet engines. The calculations were conducted on the basis of experimental concentrations of the substances and the sizes of the aerosol particles. The temperature and geometric parameters of jet engine exhausts were also taken from the literature. The absorption spectra were obtained via the line-by-line method, making use of the spectral line parameters from the authors' own high-temperature databases (for NO2 and SO2 gases) and the HITEMP 2010 database, and taking into account atmospheric transmission. Finally, the theoretical absorption spectra of the exhaust gases were plotted at temperatures of 400, 700, and 1000 K, and the impact of aerosol particles on the total exhaust spectra was estimated in spectral ranges suitable for remote sensing applications.

  2. Detection of significant differences between absorption spectra of neutral helium and low temperature photoionized helium plasmas

    SciTech Connect

    Bartnik, A.; Wachulak, P.; Fiedorowicz, H.; Fok, T.; Jarocki, R.; Szczurek, M.

    2013-11-15

    In this work, spectral investigations of photoionized He plasmas were performed. The photoionized plasmas were created by irradiation of helium stream, with intense pulses from laser-plasma extreme ultraviolet (EUV) source. The EUV source was based on a double-stream Xe/Ne gas-puff target irradiated with 10 ns/10 J Nd:YAG laser pulses. The most intense emission from the source spanned a relatively narrow spectral region below 20 nm, however, spectrally integrated intensity at longer wavelengths was also significant. The EUV radiation was focused onto a gas stream, injected into a vacuum chamber synchronously with the EUV pulse. The long-wavelength part of the EUV radiation was used for backlighting of the photoionized plasmas to obtain absorption spectra. Both emission and absorption spectra in the EUV range were investigated. Significant differences between absorption spectra acquired for neutral helium and low temperature photoionized plasmas were demonstrated for the first time. Strong increase of intensities and spectral widths of absorption lines, together with a red shift of the K-edge, was shown.

  3. Detection of significant differences between absorption spectra of neutral helium and low temperature photoionized helium plasmas

    NASA Astrophysics Data System (ADS)

    Bartnik, A.; Wachulak, P.; Fiedorowicz, H.; Fok, T.; Jarocki, R.; Szczurek, M.

    2013-11-01

    In this work, spectral investigations of photoionized He plasmas were performed. The photoionized plasmas were created by irradiation of helium stream, with intense pulses from laser-plasma extreme ultraviolet (EUV) source. The EUV source was based on a double-stream Xe/Ne gas-puff target irradiated with 10 ns/10 J Nd:YAG laser pulses. The most intense emission from the source spanned a relatively narrow spectral region below 20 nm, however, spectrally integrated intensity at longer wavelengths was also significant. The EUV radiation was focused onto a gas stream, injected into a vacuum chamber synchronously with the EUV pulse. The long-wavelength part of the EUV radiation was used for backlighting of the photoionized plasmas to obtain absorption spectra. Both emission and absorption spectra in the EUV range were investigated. Significant differences between absorption spectra acquired for neutral helium and low temperature photoionized plasmas were demonstrated for the first time. Strong increase of intensities and spectral widths of absorption lines, together with a red shift of the K-edge, was shown.

  4. Interpretation of the absorption and circular dichroic spectra of oriented purple membrane films.

    PubMed Central

    Muccio, D D; Cassim, J Y

    1979-01-01

    The absorption and circular dichroic (CD) spectra of purple membrane films in which the plane of the membranes is oriented perpendicular to the incident beam are compared with the solution spectra. This enables one to relate structural features of the purple membrane to a coordinate system as defined by a normal to the membrane plane and two mutually perpendicular in-plane axes. The film and solution absorption spectra were similar except for a relative depression in the 200 - 225-nm region of the film spectrum. However, the CD spectra showed significant differences in the visible region, where the biphasic band in the solution spectrum was replaced by a single positive band at 555 nm in the film spectrum and in the far ultraviolet region, where the 208-nm band was deleted from the film spectra of the native and regenerated membranes. Moreover, a small shoulder occurred at 208 nm in the film spectrum of the bleached membrane. The near ultraviolet spectra also showed differences, whereas the 317-nm band remained essentially the same for both spectra. Based on excitonic interpretations of the visible and far ultraviolet spectra the following conclusions were reached: (a) a relatively strong in-plane monomeric interaction occurs between te retinyl chromophore and apoprotein; (b) the helical axes of the native and regenerated membrane proteins are oriented primarily normal to the membrane plane; and (c) the helical axes of the bleached membrane proteins are tilted more in-plane than the axes of the native or regenerated membrane. Additional conclusions were that an interaction occurs between an in-plane magnetic dipole moment of the retinyl chromophore and probably an in-plane electric dipole moment of a nearby aromatic amino acid(s), and that although the membrane is anisotropic with respect to coupling between electric and magnetic moments of the aromatic amino acids, the transition dipole moments of the aromatic amino acids are not preferentially oriented in either

  5. Two-Photon-Coincidence Fluorescence Spectra of Cavity Multipolaritons: Novel Signatures of Multiexciton Generation

    PubMed Central

    Roslyak, Oleksiy; Gumbs, Godfrey; Mukamel, Shaul

    2013-01-01

    In a simulation study, we show that correlated two-dimensional frequency-resolved fluorescence spectra of a quantum dot in a microcavity provide a sensitive probe for the distribution of multiexcitons. Polariton couplings lead to a fine structure of Rabi multiplets that allow us to resolve otherwise overlapping features of the different multiexcitons. These may be used to probe multiexciton generation. PMID:20882965

  6. Filter-fluorescer measurement of low-voltage simulator x-ray energy spectra

    SciTech Connect

    Baldwin, G.T.; Craven, R.E.

    1986-01-01

    X-ray energy spectra of the Maxwell Laboratories MBS and Physics International Pulserad 737 were measured using an eight-channel filter-fluorescer array. The PHOSCAT computer code was used to calculate channel response functions, and the UFO code to unfold spectrum.

  7. S0 → Sn and S1 → Sn absorption spectra of thio-distyrylbenzenes

    NASA Astrophysics Data System (ADS)

    Baraldi, Ivan; Ginocchietti, Gabriella; Mazzucato, Ugo; Spalletti, Anna

    2007-08-01

    The molecular structures and the S0 → Sn and S1 → Sn absorption spectra of 1,4-distyrylbenzene and four thio-analogues, where the side phenyl rings are replaced by 2'-thienyl or 3'-thienyl groups and the central benzene ring is replaced by a 2,5-disubstituted thiophene ring, have been investigated by a combined theoretical and experimental approach. The rotational isomerism of these flexible molecules has been analyzed by ab initio quantum chemistry methodologies. The S0 → Sn one-photon absorption spectra and the S1 → Sn transient spectra have been calculated using the CS INDO S-CI and SDT-CI procedures. The calculations on conformational isomers indicate that the stable molecular structures are those where the quasi-single bonds of the vinylene groups have almost planar s-trans configuration. In the 1,4-compounds, there may be an equilibrium between two molecular forms of C2h and C2v symmetry in the model of planar conformations. As concerns the UV-vis absorption spectra, the importance of the cis band, as probe to investigate the molecular structure of the 2,5-compounds, has been pointed out, and the presence of an equilibrium between two rotamers in the compound bearing side 3'-thienyl groups has been confirmed. The S1 → Sn absorption spectra are interpretable only with configuration interaction calculations including the multiple excited configurations. In this respect, the role played by the H2 → L2 double excitation has been emphasized.

  8. Plant phenolics and absorption features in vegetation reflectance spectra near 1.66 μm

    NASA Astrophysics Data System (ADS)

    Kokaly, Raymond F.; Skidmore, Andrew K.

    2015-12-01

    Past laboratory and field studies have quantified phenolic substances in vegetative matter from reflectance measurements for understanding plant response to herbivores and insect predation. Past remote sensing studies on phenolics have evaluated crop quality and vegetation patterns caused by bedrock geology and associated variations in soil geochemistry. We examined spectra of pure phenolic compounds, common plant biochemical constituents, dry leaves, fresh leaves, and plant canopies for direct evidence of absorption features attributable to plant phenolics. Using spectral feature analysis with continuum removal, we observed that a narrow feature at 1.66 μm is persistent in spectra of manzanita, sumac, red maple, sugar maple, tea, and other species. This feature was consistent with absorption caused by aromatic Csbnd H bonds in the chemical structure of phenolic compounds and non-hydroxylated aromatics. Because of overlapping absorption by water, the feature was weaker in fresh leaf and canopy spectra compared to dry leaf measurements. Simple linear regressions of feature depth and feature area with polyphenol concentration in tea resulted in high correlations and low errors (% phenol by dry weight) at the dry leaf (r2 = 0.95, RMSE = 1.0%, n = 56), fresh leaf (r2 = 0.79, RMSE = 2.1%, n = 56), and canopy (r2 = 0.78, RMSE = 1.0%, n = 13) levels of measurement. Spectra of leaves, needles, and canopies of big sagebrush and evergreens exhibited a weak absorption feature centered near 1.63 μm, short ward of the phenolic compounds, possibly consistent with terpenes. This study demonstrates that subtle variation in vegetation spectra in the shortwave infrared can directly indicate biochemical constituents and be used to quantify them. Phenolics are of lesser abundance compared to the major plant constituents but, nonetheless, have important plant functions and ecological significance. Additional research is needed to advance our understanding of the spectral influences

  9. Resonance fluorescence spectra from coherently driven quantum dots coupled to slow-light photonic crystal waveguides

    NASA Astrophysics Data System (ADS)

    Roy-Choudhury, Kaushik; Mann, Nishan; Manson, Ross; Hughes, Stephen

    2016-06-01

    Using a polaron master equation approach, we investigate the resonance fluorescence spectra from coherently driven quantum dots (QDs) coupled to an acoustic phonon bath and photonic crystal waveguides with a rich local density of photon states (LDOS). Resonance fluorescence spectra from QDs in semiconductor crystals are known to show strong signatures of electron-phonon interactions, but when coupled to a structured photonic reservoir, the QD emission properties are also determined by the frequency dependence of the LDOS of the photon reservoir. Here, we investigate the simultaneous role of coupled photon and phonon baths on the characteristic Mollow triplet spectra from a strongly driven QD. As an example structured photonic reservoir, we first study a photonic crystal coupled cavity waveguide, and find that photons and phonons have counterinteracting effects near the upper mode edge of the coupled-cavity waveguide, thus establishing the importance of their separate roles in determining the emission spectra. The general theory is developed for arbitrary photonic reservoirs and is further applied to determine the resonance fluorescence spectra from a realistic, disordered W1 photonic crystal waveguide showing important photon-phonon interaction effects that are directly relevant to emerging experiments and theoretical proposals.

  10. Absorption spectra and light penetration depth of normal and pathologically altered human skin

    NASA Astrophysics Data System (ADS)

    Barun, V. V.; Ivanov, A. P.; Volotovskaya, A. V.; Ulashchik, V. S.

    2007-05-01

    A three-layered skin model (stratum corneum, epidermis, and dermis) and engineering formulas for radiative transfer theory are used to study absorption spectra and light penetration depths of normal and pathologically altered skin. The formulas include small-angle and asymptotic approximations and a layer-addition method. These characteristics are calculated for wavelengths used for low-intensity laser therapy. We examined several pathologies such as vitiligo, edema, erythematosus lupus, and subcutaneous wound, for which the bulk concentrations of melanin and blood vessels or tissue structure (for subcutaneous wound) change compared with normal skin. The penetration depth spectrum is very similar to the inverted blood absorption spectrum. In other words, the depth is minimal at blood absorption maxima. The calculated absorption spectra enable the power and irradiation wavelength providing the required light effect to be selected. Relationships between the penetration depth and the diffuse reflectance coefficient of skin (unambiguously expressed through the absorption coefficient) are analyzed at different wavelengths. This makes it possible to find relationships between the light fields inside and outside the tissue.

  11. Ab Initio Simulation of the Absorption Spectra of Photoexcited Carriers in TiO2 Nanoparticles.

    PubMed

    Nunzi, Francesca; De Angelis, Filippo; Selloni, Annabella

    2016-09-15

    We investigate the absorption spectra of photoexcited carriers in a prototypical anatase TiO2 nanoparticle using hybrid time dependent density functional theory calculations in water solution. Our results agree well with experimental transient absorption spectroscopy data and shed light on the character of the transitions. The trapped state is always involved, so that the SOMO/SUMO is the initial/final state for the photoexcited electron/hole absorption. For a trapped electron, final states in the low energy tail of the conduction band correspond to optical transitions in the IR, while final states at higher energy correspond to optical transitions in the visible. For a trapped hole, the absorption band is slightly blue-shifted and narrower in comparison to that of the electron, consistent with its deeper energy level in the band gap. Our calculations also show that electrons in shallow traps exhibit a broad absorption in the IR, resembling the feature attributed to conductive electrons in experimental spectra. PMID:27569530

  12. Theoretical electronic absorption and natural circular dichroism spectra of (-)-trans-cyclooctene

    NASA Astrophysics Data System (ADS)

    Pedersen, Thomas Bondo; Koch, Henrik

    2000-02-01

    Using the random phase approximation and coupled cluster singles and doubles linear response theory in conjunction with two basis sets of augmented double-zeta quality and two nuclear geometries, we have calculated electronic absorption and natural circular dichroism spectra of (-)-trans-cyclooctene. We present a density functional theory optimized nuclear geometry whose ground state electric dipole moment and harmonic vibrational spectrum compare well with experimental data. The coupled cluster results obtained with this nuclear geometry are in good agreement with experimental electronic spectra, although the original interpretation of the most intense low-lying band as a π→π* transition is contradicted.

  13. Two-dimensional J-spectra with absorption-mode lineshapes

    NASA Astrophysics Data System (ADS)

    Pell, Andrew J.; Keeler, James

    2007-12-01

    Two-dimensional J-spectroscopy offers the possibility of a complete separation of chemical shifts and J-couplings. However, the usefulness of the experiment is considerably reduced by the fact that peaks in the spectra have the phase-twist lineshape. We present a simple new spectroscopic method for recording J-spectra in which the peaks are both in the absorption mode and retain their natural intensities, albeit at the cost of a considerable reduction in the signal-to-noise ratio. No special data-processing is required. The method is tested on quinine, and the steroid dehydroisoandrosterone.

  14. Absorption spectra of HCFC-22 around 829/cm at atmospheric conditions

    NASA Technical Reports Server (NTRS)

    Varanasi, Prasad

    1992-01-01

    Spectral absorption coefficients of HCFC-22 have been measured around 829/cm in the laboratory at various temperature-pressure combinations chosen to represent tangent heights (as in solar-occultation experiments) or layers in the atmosphere. The data measured employing the Doppler-limited spectra resolution (about 10 exp -4/cm) of a tunable diode laser spectrometer are free of instrumental distortion and are more practical in this case than the spectral line parameters adapted in conventional line-by-line procedures for analyzing atmospheric spectra. The present data obtained with N2 as the broadening gas are shown to be directly applicable to the real atmosphere.

  15. Theoretical calculations on the electron absorption spectra of selected Polycyclic Aromatic Hydrocarbons (PAH) and derivatives

    NASA Technical Reports Server (NTRS)

    Du, Ping

    1993-01-01

    As a theoretical component of the joint effort with the laboratory of Dr. Lou Allamandola to search for potential candidates for interstellar organic carbon compound that are responsible for the visible diffuse interstellar absorption bands (DIB's), quantum mechanical calculations were performed on the electron absorption spectra of selected polycyclic aromatic hydrocarbons (PAH) and derivatives. In the completed project, 15 different species of naphthalene, its hydrogen abstraction and addition derivatives, and corresponding cations and anions were studied. Using semiempirical quantum mechanical method INDO/S, the ground electronic state of each species was evaluated with restricted Hartree-Fock scheme and limited configuration interaction. The lowest energy spin state for each species was used for electron absorption calculations. Results indicate that these calculations are accurate enough to reproduce the spectra of naphthalene cation and anion observed in neon matrix. The spectral pattern of the hydrogen abstraction and addition derivatives predicted based on these results indicate that the electron configuration of the pi orbitals of these species is the dominant determinant. A combined list of 19 absorptions calculated from 4500 A to 10,400 A were compiled and suggested as potential candidates that are relevant for the DIB's absorptions. Continued studies on pyrene and derivatives revealed the ground state symmetries and multiplicities of its neutral, anionic, and cationic species. Spectral calculations show that the cation (B(sub 3g)-2) and the anion (A(sub u)-2) are more likely to have low energy absorptions in the regions between 10 kK and 20 kK, similar to naphthalene. These absorptions, together with those to be determined from the hydrogen abstraction and addition derivatives of pyrene, can be used to provide additional candidates and suggest experimental work in the search for interstellar compounds that are responsible for DIB's.

  16. Impact of different visible light spectra on oxygen absorption and surface discoloration of bologna sausage.

    PubMed

    Böhner, Nadine; Rieblinger, Klaus

    2016-11-01

    The objective of this study was to evaluate the influence of several visible light spectra in various intensities on the oxygen absorption and surface color of sliced bologna. Sausage samples were stored in a gastight model packaging system and illuminated at 5°C with six single-colored LEDs covering the main part of the visible light spectrum. The initial oxygen level was set at 0.5% in order to simulate common residual oxygen amounts in conventional packaging. The oxygen absorption and the discoloration measured as changes in CIE a*-value were dependent from the applied light intensity. The color stability of bologna was differently affected by light of various wavelengths. The results show that the use of suitable LEDs with specific spectra for display illumination can help to reduce the light induced deterioration of cured sausages in retail markets. PMID:27343458

  17. Observationally determined Fe II oscillator strengths. [interstellar and quasar absorption spectra

    NASA Technical Reports Server (NTRS)

    Van Steenberg, M.; Shull, J. M.; Seab, C. G.

    1983-01-01

    Absorption oscillator strengths for 21 Fe II resonance lines, have been determined using a curve-of-growth analysis of interstellar data from the Copernicus and International Ultraviolet Explorer (IUE) satellites. In addition to slight changes in strengths of the far-UV lines, new f-values are reported for wavelength 1608.45, a prominent line in interstellar and quasar absorption spectra, and for wavelength 2260.08, a weak, newly identified linen in IUE interstellar spectra. An upper limit on the strength of the undetected line at 2366.867 A (UV multiplet 2) is set. Using revised oscillator strengths, Fe II column densities toward 13 OB stars are derived. The interstellar depletions, (Fe/H), relative to solar values range between factors of 10 and 120.

  18. Impact of different visible light spectra on oxygen absorption and surface discoloration of bologna sausage.

    PubMed

    Böhner, Nadine; Rieblinger, Klaus

    2016-11-01

    The objective of this study was to evaluate the influence of several visible light spectra in various intensities on the oxygen absorption and surface color of sliced bologna. Sausage samples were stored in a gastight model packaging system and illuminated at 5°C with six single-colored LEDs covering the main part of the visible light spectrum. The initial oxygen level was set at 0.5% in order to simulate common residual oxygen amounts in conventional packaging. The oxygen absorption and the discoloration measured as changes in CIE a*-value were dependent from the applied light intensity. The color stability of bologna was differently affected by light of various wavelengths. The results show that the use of suitable LEDs with specific spectra for display illumination can help to reduce the light induced deterioration of cured sausages in retail markets.

  19. Source brightness fluctuation correction of solar absorption Fourier Transform mid infrared spectra

    NASA Astrophysics Data System (ADS)

    Ridder, T.; Warneke, T.; Notholt, J.

    2011-01-01

    Solar absorption Fourier Transform infrared spectrometry is considered a precise and accurate method for the observation of trace gases in the atmosphere. The precision and accuracy of such measurements are dependent on the stability of the light source. Fluctuations in the source brightness reduce the precision and accuracy of the trace gas concentrations, but cannot always be avoided. Thus, a strong effort is made within the community to reduce the impact of source brightness fluctuations by applying a correction on the spectra following the measurements. So far, it could be shown that the precision and accuracy of CO2 total column concentrations could be improved by applying a source brightness fluctuation correction to spectra in the near infrared spectral region. The analysis of trace gas concentrations obtained from spectra in the mid infrared spectral region is fundamental. However, spectra below 2000 cm-1 are generally considered uncorrectable, if they are measured with a MCT detector. Such measurements introduce an unknown offset to MCT interferograms, which prevents a source brightness fluctuation correction. Here, we show a method of source brightness fluctuation correction, which can be applied on spectra in the whole infrared spectral region including spectra measured with a MCT detector. We present a solution to remove the unknown offset in MCT interferograms allowing MCT spectra for an application of source brightness fluctuation correction. This gives an improvement in the quality of MCT spectra and we demonstrate an improvement in the retrieval of O3 profiles and total column concentrations. For a comparison with previous studies, we apply our source brightness fluctuation correction method on spectra in the near infrared spectral region and show an improvement in the retrieval of CO2 total column concentrations.

  20. Multiphoton fluorescence spectra and lifetimes of biliverdins and their protein-associated complex

    NASA Astrophysics Data System (ADS)

    Huang, Chin-Jie; Wu, Cheng-Ham; Liu, Tzu-Ming

    2012-03-01

    To investigate whether endogenous biliverdins can serve as a fluorescence metabolic marker in cancer diagnosis, we measured their multiphoton fluorescence spectra and lifetimes with femtosecond Cr:forsterite laser. Excited at 1230nm, the two-photon fluorescence of biliverdins peaks around 670nm. The corresponding lifetime (<100ps) was much shorter than those of porphyrins (~10ns), which is another commonly present metabolites in living cells. Further mixing biliverdins with proteins like fetal bovine serum (FBS), biliverdins reductase A (BVRA), or heme oxygenase-1 (HO-1), the yields of red autofluorescences didn't change a lot, but the corresponding lifetimes with HO-1 and BSA were lengthened to 200~300ps. This indicates that biliverdin can have an association with these proteins and change its lifetime. These spectral and temporal characteristics of fluorescence make biliverdin a potential marker fluorophore for hyperspectral diagnosis on the heme catabolism in human cells or tissues.

  1. Measurements of niobium absorption spectra in plasmas with nearly full M-shell configurations

    NASA Astrophysics Data System (ADS)

    Hoarty, D. J.; Harris, J. W. O.; Graham, P.; Davidson, S. J.; James, S. F.; Crowley, B. J. B.; Clark, E. L.; Smith, C. C.; Upcraft, L.

    2007-10-01

    A systematic study has been carried out on the changes in the L-shell absorption structure of niobium as a result of changing the population of the n = 3 shell from full to having vacancies in the 3d level. The niobium spectra were measured in the 2-3 keV frequency range, which spanned the 2p-nd transitions where 3 ≤ n ≤ 11. In addition to the detailed structure in these arrays the data also show 2s-4p and 2p-4s transitions and the bound-free L edge. The frequencies and widths of transition arrays, transmission between arrays, and the absorption due to the bound-free edge, can be seen in the data. The sample conditions were found from a combination of two-dimensional radiation-hydrodynamics calculations using the AWE NYM code and flux measurements using X-ray diodes, measurements of 1s-2p absorption spectra in aluminium and mixed aluminium/niobium samples. The electron temperature error, inferred from the modelling, is ±2 eV, with a density error of 30%. The data were recorded over the temperature range from ˜28 to 45 eV and show marked changes in the spectra over this range. The data were compared to spectra predicted by the AWE CASSANDRA [B.J.B. Crowley, J.W.O. Harris, J. Quant. Spectrosc. Radiat. Transfer 71 (2000) p. 257] opacity code. The calculated spectra were able to reproduce the measurements reasonably well. However, there are some differences in line positions that cannot be accounted for by gradients and there are differences in the array structure in the prediction and the measurements, with additional structure predicted but not seen in the measurements. There is also lower transmission on the blue side of the 2p-3d transition arrays compared to prediction.

  2. Near infrared cavity enhanced absorption spectra of atmospherically relevant ether-1, 4-Dioxane

    NASA Astrophysics Data System (ADS)

    Chandran, Satheesh; Varma, Ravi

    2016-01-01

    1, 4-Dioxane (DX) is a commonly found ether in industrially polluted atmosphere. The near infrared absorption spectra of this compound has been recorded in the region 5900-8230 cm- 1 with a resolution of 0.08 cm- 1 using a novel Fourier transform incoherent broadband cavity-enhanced absorption spectrometer (FT-IBBCEAS). All recorded spectra were found to contain regions that are only weakly perturbed. The possible combinations of fundamental modes and their overtone bands corresponding to selected regions in the measured spectra are tabulated. Two interesting spectral regions were identified as 5900-6400 cm- 1 and 8100-8230 cm- 1. No significant spectral interference due to presence of water vapor was observed suggesting the suitability of these spectral signatures for spectroscopic in situ detection of DX. The technique employed here is much more sensitive than standard Fourier transform spectrometer measurements on account of long effective path length achieved. Hence significant enhancement of weaker absorption lines above the noise level was observed as demonstrated by comparison with an available measurement from database.

  3. The use of commercial glass as a potential gamma accidental dosimeter through the absorption spectra

    NASA Astrophysics Data System (ADS)

    Kharita, M. H.; Yousef, S.; Bakr, S.

    2012-05-01

    Various types of commercial glass (ordinary windows, cathode ray tubes, glass kitchenware) have been studied as potential accidental radiation dosimeters. The proposed method utilizes the changes in the glasses' absorption spectra as a result of irradiation. A 60Co gamma irradiation cell has been used to irradiate samples with doses ranging from 5 to 200 Gy. The transmittance was measured using a photospectrometer (UV-visible spectrometry). The results demonstrate that the transmittance spectra of most of the glass samples change in linear proportion to the exposure dose. Moreover, the study considers the fading effect on the absorption spectra of the irradiated samples for fading times up to 100 days at room temperature. The results of this work demonstrate that several widely used types of glass can be used as high-dose accidental dosimeters for doses ranging between 8 and 200 Gy. A reasonable calibration line can be established for any irradiated glass sample by heating, re-irradiating with standard doses and measuring the related absorption coefficient. Further investigations are needed to decrease the minimum detectable dose of the proposed method and to study the effect of glass composition on radiation response.

  4. Hot Experimental Absorption Spectra of CH_4 in the Pentad and Octad Region

    NASA Astrophysics Data System (ADS)

    Hargreaves, Robert J.; Dulick, Michael; Bernath, Peter F.

    2014-06-01

    We present comprehensive line lists of CH_4 at high temperatures for the pentad and octad region (2400-5000 wn). These spectra improve on our previous emission measurements for this region by using a new quartz sample cell in conjunction with a tube furnace (pictured). Ten temperatures have been recorded from room temperature up to 1000°C and our technique involves the acquisition of four separate Fourier transform infrared spectra at each temperature, thus accounting for both the emission and absorption of the molecule and the cell. By combining these four spectra we obtain true transmission spectra of hot CH_4 in this region. Analysis of this set of spectra enables the production of a line list that includes the position, intensity and empirical lower state energy. Our spectra and line lists can be used directly to model planetary atmospheres and brown dwarfs. Hargreaves, R.J., Beale, C.A., Michaux, L., Irfan, M., & Bernath, P.F. 2012, ApJ, 757, 46

  5. Optical absorption spectra of substitutional Co2+ ions in Mgx Cd1-x Se alloys

    NASA Astrophysics Data System (ADS)

    Jin, Moon-Seog; Kim, Chang-Dae; Jang, Kiwan; Park, Sang-An; Kim, Duck-Tae; Kim, Hyung-Gon; Kim, Wha-Tek

    2006-09-01

    Optical absorption spectra of substitutional Co2+ ions in Mgx Cd1-x Se alloys were investigated in the composition region of 0.0 x 0.4 and in the wavelength region of 300 to 2500 nm at 4.8 K and 290 K. We observed several absorption bands in the wavelength regions corresponding to the 4A2(4F) 4T1(4P) transition and the 4A2(4F) 4T1(4F) transition of Co2+ at a tetrahedral Td point symmetry point in the host crystals, as well as unknown absorption bands. The several absorption bands were analyzed in the framework of the crystal-field theory along with the second-order spin-orbit coupling. The unknown absorption bands were assigned as due to phonon-assisted absorption bands. We also investigated the variations of the crystal-field parameter Dq and the Racah parameter B with composition x in the Mgx Cd1-x Se system. The results showed that the crystal-field parameter (Dq ) increases, on the other hand, the Racah parameter (B ) decreases with increasing composition x, which may be connected with an increase in the covalency of the metal-ligand bond with increasing composition x in the Mgx Cd1-x Se system.

  6. Twin-peaks absorption spectra of excess electron in ionic liquids

    NASA Astrophysics Data System (ADS)

    Musat, Raluca M.; Kondoh, Takafumi; Yoshida, Yoichi; Takahashi, Kenji

    2014-07-01

    The solvated electron in room temperature ionic liquids (RTILs) has been the subject of several investigations and several reports exist on its nature and absorption spectrum. These studies concluded that the solvated electron exhibits an absorption spectrum peaking in the 1000-1400 nm region; a second absorption band peaking in the UV region has been assigned to the hole or dication radicals simultaneously formed in the system. Here we report on the fate of the excess electron in the ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, P14+/NTf2- using nanosecond pulse radiolysis. Scavenging experiments allowed us to record and disentangle the complex spectrum measured in P14+/NTf2-. We identified a bi-component absorption spectrum, due to the solvated electron, the absorption maxima located at 1080 nm and around 300 nm, as predicted by previous ab-initio molecular dynamics simulations for the dry excess electron. We also measured the spectra using different ionic liquids and confirmed the same feature of two absorption peaks. The present results have important implications for the characterization of solvated electrons in ionic liquids and better understanding of their structure and reactivity.

  7. Intelligent information extraction from reflectance spectra Absorption band positions. [application to laboratory and earth-based telescope spectra

    NASA Technical Reports Server (NTRS)

    Huguenin, R. L.; Jones, J. L.

    1986-01-01

    A multiple high-order derivative analysis algorithm has been developed which can automatically extract absorption band positions from low-quality reflectance spectra with little degredation of accuracy. Overlapping bands with comparable widths and intensities can be resolved whose centers are as close as 0.3-0.5 W, with safer resolution limits of 0.6-1.0 W band center separations suggested for overlapping bands that are dissimilar. The segment length for smoothing is continually adjusted to about 0.5 W to minimize signal distortion, and a spectral pattern recognition algorithm predicts the signal spectrum and calculates approximate W across the spectrum using its second derivative. A single-pass cubic spline is applied to the smoothed data, and a sliding segment sixth-order polynomial is fit to the spectrum, with the length of the segment being continuously locally adjusted to 1.0 W across the spectrum. Good reliability and consistency of the algorithm is demonstrated with application to laboratory and earth-based telescope spectra.

  8. Laser Induced Chlorophyll Fluorescence Spectra of Cajanus Cajan L Plant Growing Under Cadmium Stress

    NASA Astrophysics Data System (ADS)

    Gopal, Ram; Pandey, J. K.

    2010-06-01

    Laser-induced Chlorophyll fluorescence (LICF) spectra of Cajanus cajan L leaves treated with different concentrations of Cd (0.05, 0.5 and 1 mM) are recorded at 10 and 20 days after first treatment of cadmium. LICF spectra are recorded in the region of 650-780 nm using violet diode laser (405 nm). LICF spectra of plant leaves show two maxima near 685 and 730nm. Fluorescence induction kinetics (FIK) curve are recorded at 685 and 730 nm with red diode laser (635 nm) for excitation. The fluorescence intensity ratios (FIR) F685/F730 are calculated from LICF spectra and vitality index (Rfd) are determined from FIK curve. FIR and Rfd value are good stress indicator of plant health. These parameters along with chlorophyll content are used to analyze the effect of Cd on wheat plants. The result indicates that higher concentrations of Cd hazardous for photosynthetic activity and health of Arhar plants. The lower concentration of 0.05 mM shows stimulatory response up to 10 days while after 20 days this concentration also shows inhibitory response. R. Gopal, K. B. Mishra, M. Zeeshan, S. M. Prasad, and M. M. Joshi Curr. Sci., 83, 880, 2002 K. B. Mishra and R. Gopal Int. J. Rem. Sen., 29, 157, 2008 R. Maurya, S. M. Prasad, and R. Gopal J. Photochem. Photobio. C: Photochem. Rev., 9, 29, 2008

  9. Photon-photon absorption and the uniqueness of the spectra of active galactic nuclei

    NASA Technical Reports Server (NTRS)

    Kazanas, D.

    1984-01-01

    The effects of the feedback of e(+)-e(-) pair reinjection in a plasma due to photon-photon absorption of its own radiation was examined. Under the assumption of continuous electron injection with a power law spectrum E to the minus gamma power and Compton losses only, it is shown that for gamma 2 the steady state electron distribution function has a unique form independent of the primary injection spectrum. This electron distribution function can, by synchrotron emission, reproduce the general characteristics of the observed radio to optical active galactic nuclei spectra. Inverse Compton scattering of the synchrotron photons by the same electron distribution can account for their X-ray spectra, and also implies gamma ray emission from these objects. This result is invoked to account for the similarity of these spectra, and it is consistent with observations of the diffuse gamma ray background.

  10. Time-resolved Absorption Spectra of the Laser-dressed Hydrogen Atom

    NASA Astrophysics Data System (ADS)

    Murakami, Mitsuko; Chu, Shih-I.

    2013-05-01

    A theoretical study of the transient absorption spectra for the laser-dressed hydrogen atom based on the accurate numerical solution of the time-dependent Schrödinger equation is presented. The timing of absorption is controlled by the time delay between an isolated extreme ultraviolet (XUV) pulse and a dressing infrared (IR) field. We identify two different kinds of physical processes in the spectra. One is the formation of dressed states, signified by the appearance of sidebands between the XUV absorption lines separated by one IR-photon energy. We show that their population is maximized when the XUV pulse coincides with the zero-crossing of the IR field, and that their energy can be manipulated by using a chirped IR field. The other process is the dynamical AC Stark shift induced by the IR field and probed by the XUV pulse. Our calculations indicate that the accidental degeneracy of the hydrogen atom leads to the multiple splittings of each XUV absorption line whose separations change in response to a slowly-varying IR envelope. Furthermore, we observe the Autler-Townes doublets for the n=2 and 3 states using the 656 nm dressing field, but their separation does not agree with the prediction by the conventional 3-level model that neglects the dynamical AC Stark effects.

  11. Absorption spectra and photoresponse observation of Cu2O thin film photoanodes

    NASA Astrophysics Data System (ADS)

    Mani, Endri; Garuthara, Rohana

    2014-03-01

    Electrodeposition was used to deposit Cu2O thin films on ITO substrates. The deposited Cu2O films were characterized by photocurrent, absorption and reflectance spectroscopy. Photoresponse of the film clearly indicated n-type behavior of Cu2O in photoelectrochemical cells. The effects of chlorine doped photoanodes deposited in different solution pH on the magnitude of their photocurrent are studied. The low temperature absorption spectra of chlorine doped Cu2O films are found to depend on the solution pH in the range 10.0-7.5. Optical absorption spectra of Cu2O films were measured in the temperature range 79K - 295K. The Urbach's tail was observed for n-type conductive Cu2O films in the temperature range 79K to 295K. The Urbach's energy as a function of temperature for Cu2O films were studied. The results will be discussed with emphasis on the reflectance, absorption and photoresponse observation.

  12. Determining CDOM Absorption Spectra in Diverse Aquatic Environments Using a Multiple Pathlength, Liquid Core Waveguide System

    NASA Technical Reports Server (NTRS)

    Miller, Richard L.; Belz, Mathias; DelCastillo, Carlos; Trzaska, Rick

    2001-01-01

    We evaluated the accuracy, sensitivity and precision of a multiple pathlength, liquid core waveguide (MPLCW) system for measuring colored dissolved organic matter (CDOM) absorption in the UV-visible spectral range (370-700 nm). The MPLCW has four optical paths (2.0, 9.8, 49.3, and 204 cm) coupled to a single Teflon AF sample cell. Water samples were obtained from inland, coastal and ocean waters ranging in salinity from 0 to 36 PSU. Reference solutions for the MPLCW were made having a refractive index of the sample. CDOM absorption coefficients, aCDOM, and the slope of the log-linearized absorption spectra, S, were compared with values obtained using a dual-beam spectrophotometer. Absorption of phenol red secondary standards measured by the MPLCW at 558 nm were highly correlated with spectrophotometer values and showed a linear response across all four pathlengths. Values of aCDOM measured using the MPLCW were virtually identical to spectrophotometer values over a wide range of concentrations. The dynamic range of aCDOM for MPLCW measurements was 0.002 - 231.5 m-1. At low CDOM concentrations spectrophotometric aCDOM were slightly greater than MPLCW values and showed larger fluctuations at longer wavelengths due to limitations in instrument precision. In contrast, MPLCW spectra followed an exponential to 600 nm for all samples.

  13. On the potential usefulness of Fourier spectra of delayed fluorescence from plants.

    PubMed

    Guo, Ya; Tan, Jinglu

    2014-12-09

    Delayed fluorescence (DF) from photosystem II (PSII) of plants can be potentially used as a biosensor for the detection of plant physiological status and environmental changes. It has been analyzed mainly in the time domain. Frequency-domain analysis through Fourier transform allows viewing a signal from another angle, but the usefulness of DF spectra has not been well studied. In this work, experiments were conducted to show the differences and similarities in DF spectra of different plants with short pulse excitation. The DF spectra show low-pass characteristics with first-order attenuation of high frequencies. The results also show that the low-frequency components differ while the high-frequency components are similar. These may imply the potential usefulness of Fourier spectra of DF to analyze photoelectron transport in plants and classify samples.

  14. Delayed fluorescence spectra of intact leaves photoexcited by sunlight measured with a multichannel Fourier-transform chemiluminescence spectrometer

    NASA Astrophysics Data System (ADS)

    Akita, Saeka; Yano, Ayako; Ishii, Hiroshi; Satoh, Chikahiro; Akai, Nobuyuki; Nakata, Munetaka

    2013-06-01

    Delayed fluorescence spectra of intact leaves of Green pak choi (Brassica rapa var. chinensis) were measured with a multichannel Fourier-transform chemiluminescence spectrometer, which we developed recently. The intact samples, photoexcited by sunlight without artificial light sources, showed delayed fluorescence around 740 nm with a lifetime of ˜6 s. The observed spectra were deconvoluted into two Gaussian bands: the delayed fluorescence from photosystem II and photosystem I complexes. Their relative intensities depended on the chlorophyll concentration, but their wavelengths were unchanged.

  15. Bands separation in fluorescence spectra of ketocyanine dyes: evidence for their complex formation with monohydric alcohols

    NASA Astrophysics Data System (ADS)

    Pivovarenko, V. G.; Klueva, A. V.; Doroshenko, A. O.; Demchenko, A. P.

    2000-07-01

    In the studies of binary solvent systems containing non-polar (toluene) and polar proton-donating components (monohydric alcohols) using ketocyanine dyes of 2,5-di-benzylidene-cyclopentanone-1 type as solvent polarity probes, we found that in addition to common solvent polarity-dependent shifts of fluorescence spectra, at low alcohol concentrations there appear two new well-resolved spectral bands. They are attributed to the emission of hydrogen bonded complexes of 1:1 and 1:2 type. Effective constants for hydrogen bond complex formation were estimated for them from the fluorescence titration data.

  16. Magnetic fluorescent lamp having reduced ultraviolet self-absorption

    DOEpatents

    Berman, Samuel M.; Richardson, Robert W.

    1985-01-01

    The radiant emission of a mercury-argon discharge in a fluorescent lamp assembly (10) is enhanced by providing means (30) for establishing a magnetic field with lines of force along the path of electron flow through the bulb (12) of the lamp assembly, to provide Zeeman splitting of the ultraviolet spectral line. Optimum results are obtained when the magnetic field strength causes a Zeeman splitting of approximately 1.7 times the thermal line width.

  17. Dual fluorescence excitation spectra of methyl salicylate in a free jet

    NASA Astrophysics Data System (ADS)

    Heimbrook, Lou Ann; Kenny, Jonathan E.; Kohler, Bryan E.; Scott, Gary W.

    1981-11-01

    Separate fluorescence excitation spectra of the blue- and UV-emitting forms of methyl salicylate cooled in a free-jet expansion are reported. This study represents the first observation of the detailed vibrational structure of these transitions. The two excitation spectra have no features in common, and their intensity patterns are very different. Many individual lines are ˜2 cm-1 wide (nearly laser limited), although in the excitation spectrum of the UV emission, spectral congestion persists at high energies despite the high degree of cooling. (AIP)

  18. Predicting accurate fluorescent spectra for high molecular weight polycyclic aromatic hydrocarbons using density functional theory

    NASA Astrophysics Data System (ADS)

    Powell, Jacob; Heider, Emily C.; Campiglia, Andres; Harper, James K.

    2016-10-01

    The ability of density functional theory (DFT) methods to predict accurate fluorescence spectra for polycyclic aromatic hydrocarbons (PAHs) is explored. Two methods, PBE0 and CAM-B3LYP, are evaluated both in the gas phase and in solution. Spectra for several of the most toxic PAHs are predicted and compared to experiment, including three isomers of C24H14 and a PAH containing heteroatoms. Unusually high-resolution experimental spectra are obtained for comparison by analyzing each PAH at 4.2 K in an n-alkane matrix. All theoretical spectra visually conform to the profiles of the experimental data but are systematically offset by a small amount. Specifically, when solvent is included the PBE0 functional overestimates peaks by 16.1 ± 6.6 nm while CAM-B3LYP underestimates the same transitions by 14.5 ± 7.6 nm. These calculated spectra can be empirically corrected to decrease the uncertainties to 6.5 ± 5.1 and 5.7 ± 5.1 nm for the PBE0 and CAM-B3LYP methods, respectively. A comparison of computed spectra in the gas phase indicates that the inclusion of n-octane shifts peaks by +11 nm on average and this change is roughly equivalent for PBE0 and CAM-B3LYP. An automated approach for comparing spectra is also described that minimizes residuals between a given theoretical spectrum and all available experimental spectra. This approach identifies the correct spectrum in all cases and excludes approximately 80% of the incorrect spectra, demonstrating that an automated search of theoretical libraries of spectra may eventually become feasible.

  19. The effect of implanting boron on the optical absorption and electron paramagnetic resonance spectra of silica

    NASA Astrophysics Data System (ADS)

    Magruder, R. H.; Stesmans, A.; Weeks, R. A.; Weller, R. A.

    2008-09-01

    Silica samples (type III, Corning 7940) were implanted with B using multiple energies to produce a layer ˜600 nm thick in which the concentration of B ranged from 0.034 to 2.04 at. %. Optical absorption spectra were measured from 1.8 to 6.5 eV. Electron paramagnetic resonance (EPR) measurements were generally made at ˜20.3 and 33 GHz for sample temperatures ranging from 77 to 100 K. Based on the EPR spectra three types of defects, namely, Eγ', the E'-type 73 G split doublet (E73'), and the peroxyradical (POR) were identified. No oxygen-associated hole centers (OHCs) nor specific B-associated paramagnetic defects were detected, not even at the largest B concentration of 2.04 at. %. Unlike previous assignments, there was no correlation between the 4.83 eV optical absorption band and the observed PORs. From these results, we infer that in addition to POR, there is at least one additional Si-related state absorbing in the 4.8-4.9 eV range that is likely diamagnetic. The 5.85 eV optical absorption band is found to be due to the Eγ' and E73' centers, with, in average, quite similar oscillator strengths inferred as before. Both the optical absorption and the electron spin resonance data can be satisfactorily explained without the need for specific B-associated defect site (s). As no OHCs are detected by ESR, these do not seem to make a detectable contribution to the optical spectra.

  20. Energy and optical absorption spectra of endohedral metallofullerenes with Gd or Ho as strongly correlated π-electron systems

    NASA Astrophysics Data System (ADS)

    Bubnov, V. P.; Kareev, I. E.; Lobanov, B. V.; Murzashev, A. I.; Nekrasov, V. M.

    2016-08-01

    Isomerically pure endohedral metallofullerenes Gd@C82(C2v), Ho@C82( C 2 v ), and their monoanions have been synthesized and separated. The optical absorption spectra of solutions of obtained compounds in o-dichlorobenzene have been studied. Within the Hubbard model, the energy spectrum of isomer of C 2 v symmetry (no. 9) of fullerene C82 has been calculated. Based on the obtained spectrum, optical absorption spectra of endohedral metallofullerenes Gd@C82 and Ho@C82 and their monoanions have been simulated. The calculated optical absorption spectra have been compared with experimental ones; it has been found that qualitative agreement between them is observed.

  1. Narrow C IV absorption doublets on quasar spectra of the Baryon Oscillation Spectroscopic Survey

    NASA Astrophysics Data System (ADS)

    Chen, Zhi-Fu; Gu, Qiu-Sheng; Zhou, Luwenjia; Chen, Yan-Mei

    2016-11-01

    In this paper, we extend our work of Papers I and II, which are assigned to systematically survey C IV λλ1548,1551 narrow absorption lines (NALs) with zabs ≪ zem on quasar spectra of the Baryon Oscillation Spectroscopic Survey (BOSS) to collect C IV NALs with zabs ≈ zem from blue to red wings of C IV λ1549 emission lines. Together with Papers I and II, we have collected a total number of 41 479 C IV NALs with 1.4544 ≤ zabs ≤ 4.9224 in surveyed spectral region redward of Lyα until red wing of C IV λ1549 emission line. We find that the stronger C IV NALs tend to be the more saturated absorptions, and associated systems (zabs ≈ zem) seem to have larger absorption strengths when compared to intervening ones (zabs ≪ zem). The redshift density evolution behaviour of absorbers (the number of absorbers per redshift path) is similar to the history of the cosmic star formation. When compared to the quasar-frame velocity (β) distribution of Mg II absorbers, the β distribution of C IV absorbers is broader at β ≈ 0, shows longer extended tail, and exhibits a larger dispersion for environmental absorptions. In addition, for associated C IV absorbers, we find that low-luminosity quasars seem to exhibit smaller β and stronger absorptions when compared to high-luminosity quasars.

  2. Real-time atmospheric absorption spectra for in-flight tuning of an airborne dial system

    NASA Technical Reports Server (NTRS)

    Dombrowski, M.; Walden, H.; Schwemmer, G. K.; Milrod, J.; Korb, C. L.

    1986-01-01

    Real-time measurements of atmospheric absorption spectra are displayed and used to precisely calibrate and fix the frequency of an Alexandrite laser to specific oxygen absorption features for airborne Differential Absorption Lidar (DIAL) measurements of atmospheric pressure and temperature. The DIAL system used contains two narrowband tunable Alexandrite lasers: one is electronically scanned to tune to oxygen absorption features for on-line signals while the second is used to obtain off-line (nonabsorbed) atmospheric return signals. The lidar operator may select the number of shots to be averaged, the altitude, and altitude interval over which the signals are averaged using single key stroke commands. The operator also determines exactly which oxygen absorption lines are scanned by comparing the line spacings and relative strengths with known line parameters, thus calibrating the laser wavelength readout. The system was used successfully to measure the atmospheric pressure profile on the first flights of this lidar, November 20, and December 9, 1985, aboard the NASA Wallops Electra aircraft.

  3. Far wing depolarization of light - Generalized absorption profiles. [in laser fluorescence spectroscopy of Sr vapor

    NASA Technical Reports Server (NTRS)

    Thomann, P.; Burnett, K.; Cooper, J.

    1981-01-01

    An absorption (and/or emission) event which takes place during a strong collision is called a 'correlated event'. It is discussed how correlated events affect the far red wing depolarization of fluorescence. Attention is given to an atomic vapor which is irradiated by linearly polarized light of a frequency on the red side of the resonance line. Two limiting cases are considered, corresponding to excitation in the impact region and in the quasi-static wing. In the quasi-static wing, absorption of a photon followed by fluorescence (rather than Rayleigh scattering), occurs mostly during a collision. Correlated events dominate the scattering process. Expressions derived for the polarization of the fluorescent light are applied to far red wing depolarization. It is found that the polarization of the fluorescent light does not go to zero in the far wing, but depends crucially on the detailed nature of the anisotropy in the long-range part of the interatomic potential.

  4. Effect of anthocyanins, carotenoids, and flavonols on chlorophyll fluorescence excitation spectra in apple fruit: signature analysis, assessment, modelling, and relevance to photoprotection.

    PubMed

    Merzlyak, Mark N; Melø, Thor Bernt; Naqvi, K Razi

    2008-01-01

    Whole apple fruit (Malus domestica Borkh.) widely differing in pigment content and composition has been examined by recording its chlorophyll fluorescence excitation and diffuse reflection spectra in the visible and near UV regions. Spectral bands sensitive to the pigment concentration have been identified, and linear models for non-destructive assessment of anthocyanins, carotenoids, and flavonols via chlorophyll fluorescence measurements are put forward. The adaptation of apple fruit to high light stress involves accumulation of these protective pigments, which absorb solar radiation in broad spectral ranges extending from UV to the green and, in anthocyanin-containing cultivars, to the red regions of the spectrum. In ripening apples the protective effect in the blue region could be attributed to extrathylakoid carotenoids. A simple model, which allows the simulation of chlorophyll fluorescence excitation spectra in the visible range and a quantitative evaluation of competitive absorption by anthocyanins, carotenoids, and flavonols, is described. Evidence is presented to support the view that anthocyanins, carotenoids, and flavonols play, in fruit with low-to-moderate pigment content, the role of internal traps (insofar as they compete with chlorophylls for the absorption of incident light in specific spectral bands), affecting thereby the shape of the chlorophyll fluorescence excitation spectrum.

  5. [Time resolved UV-Vis absorption spectra of quercetin reacting with various concentrations of sodium hydroxide].

    PubMed

    Yang, Li-Jun; Li, Ping; Gao, Yan-Jun; Li, Hui-Feng; Wu, Da-Cheng; Li, Rui-Xia

    2009-06-01

    A real time investigation of chemical reaction process of quercetin with various concentrations of sodium hydroxide was performed by using an intensified spectroscopic detector ICCD. The time resolved UV-Vis absorption spectra of 5 x 10(-5) mol x L(-1) quercetin respectively reacting with sodium hydroxide at concentrations of 2, 0.2, 0.1, 0.04 and 0.02 mol x L(-1) were acquired. A total of 200 spectra with the same exposure time of 0.1 ms for each spectrum but different time interval between two consecutive spectra were recorded for each reaction. The first 50 spectra have the time interval of 20 ms, the next 50 have 1 s, and the last 100 have 2 s. Results indicate that quercetin reacted with sodium hydroxide easily and there was an intermediate product formed during the reaction, with different concentrations of reactants, the changes of absorption bands were the same, but the moments at which the changes happened were different and the total reaction time was various from 1 s to 100 s. Spectra recorded showed the disappearing process of the typical bands centered at 254 and 374 nm of pure quercetin, the growing and disappearing processes of a new band centered at 427 nm of the intermediate product, and the growing process of the new band centered at 314 nm of the final product obviously. No other transient spectroscopic data are currently available on the reaction of quercrtin with sodium hydroxide, the results obtained in the present work provide useful experimental data for the study of the microscopic process of the reaction.

  6. Assignment of bacteriochlorophyll a ligation state from absorption and resonance raman spectra

    SciTech Connect

    Callahan, P.M.; Cotton, T.M.

    1987-11-11

    Absorption and Soret excitation resonance Raman (RR) spectra have been obtained for a series of coordination forms on monomeric bacteriochlorophyll a (BChl a). Strong and moderate intensity bands are observed in the RR spectrum at 1609 and 1530 cm/sup -1/ for five-coordinate species, which shift to 1595 and 1512 cm/sup -1/, respectively, in the six-coordinate form. These coordination-sensitive vibrations are independent of the nature of the axial ligand and are suggested to have significant C/sub a/ C/sub m/ character, while several other less intense coordination-sensitive bands at 1463, 1444, and 1375 cm/sup -1/ are considered to arise from C/sub b/C/sub b/ and C/sub a/N stretching vibrations. These coordination-sensitive RR bands were used to determine BChl a ligation state in the solvents used, and structure correlations based on absorption maxima have been developed. The Q/sub x/ absorption band position is sensitive not only to BChl a Mg/sup 2 +/ coordination number but also to the nature of the axial ligand, i.e., oxygen, sulfur, or nitrogen. Q/sub x/ maxima are observed at 570, 575-580, and 582 nm for five-coordinate oxygen, sulfur, and nitrogen ligands, respectively, and at 590-595 and 605-612 nm, for six-coordinate oxygen and nitrogen species, respectively. The Q/sub y/ absorption maximum is insensitive to coordination number changes but is dependent on the nature of the axial ligand: 770 nm for oxygen ligand(s) and 775 nm for nitrogen ligand(s). A similar series of absorption and Soret excitation RR spectra were obtained for the demetalated form of BChl a, BPheo a.

  7. Calculation of UV attenuation and colored dissolved organic matter absorption spectra from measurements of ocean color

    NASA Astrophysics Data System (ADS)

    Johannessen, S. C.; Miller, W. L.; Cullen, J. J.

    2003-09-01

    The absorption of ultraviolet and visible radiation by colored or chromophoric dissolved organic matter (CDOM) drives much of marine photochemistry. It also affects the penetration of ultraviolet radiation (UV) into the water column and can confound remote estimates of chlorophyll concentration. Measurements of ocean color from satellites can be used to predict UV attenuation and CDOM absorption spectra from relationships between visible reflectance, UV attenuation, and absorption by CDOM. Samples were taken from the Bering Sea and from the Mid-Atlantic Bight, and water types ranged from turbid, inshore waters to the Gulf Stream. We determined the following relationships between in situ visible radiance reflectance, Lu/Ed (λ) (sr-1), and diffuse attenuation of UV, Kd(λ) (m-1): Kd(323nm) = 0.781[Lu/Ed(412)/Lu/Ed(555)]-1.07; Kd(338nm) = 0.604[Lu/Ed(412)/Lu/Ed(555)]-1.12; Kd(380 nm) = 0.302[Lu/Ed(412)/Lu/Ed(555)]-1.24. Consistent with published observations, these empirical relationships predict that the spectral slope coefficient of CDOM absorption increases as diffuse attenuation of UV decreases. Excluding samples from turbid bays, the ratio of the CDOM absorption coefficient to Kd is 0.90 at 323 nm, 0.86 at 338 nm, and 0.97 at 380 nm. We applied these relationships to SeaWiFS images of normalized water-leaving radiance to calculate the CDOM absorption and UV attenuation in the Mid-Atlantic Bight in May, July, and August 1998. The images showed a decrease in UV attenuation from May to August of approximately 50%. We also produced images of the areal distribution of the spectral slope coefficient of CDOM absorption in the Georgia Bight. The spectral slope coefficient increased offshore and changed with season.

  8. Plant phenolics and absorption features in vegetation reflectance spectra near 1.66 μm

    USGS Publications Warehouse

    Kokaly, Raymond F.; Skidmore, Andrew K

    2015-01-01

    Past laboratory and field studies have quantified phenolic substances in vegetative matter from reflectance measurements for understanding plant response to herbivores and insect predation. Past remote sensing studies on phenolics have evaluated crop quality and vegetation patterns caused by bedrock geology and associated variations in soil geochemistry. We examined spectra of pure phenolic compounds, common plant biochemical constituents, dry leaves, fresh leaves, and plant canopies for direct evidence of absorption features attributable to plant phenolics. Using spectral feature analysis with continuum removal, we observed that a narrow feature at 1.66 μm is persistent in spectra of manzanita, sumac, red maple, sugar maple, tea, and other species. This feature was consistent with absorption caused by aromatic C-H bonds in the chemical structure of phenolic compounds and non-hydroxylated aromatics. Because of overlapping absorption by water, the feature was weaker in fresh leaf and canopy spectra compared to dry leaf measurements. Simple linear regressions of feature depth and feature area with polyphenol concentration in tea resulted in high correlations and low errors (% phenol by dry weight) at the dry leaf (r2 = 0.95, RMSE = 1.0%, n = 56), fresh leaf (r2 = 0.79, RMSE = 2.1%, n = 56), and canopy (r2 = 0.78, RMSE = 1.0%, n = 13) levels of measurement. Spectra of leaves, needles, and canopies of big sagebrush and evergreens exhibited a weak absorption feature centered near 1.63 μm, short ward of the phenolic compounds, possibly consistent with terpenes. This study demonstrates that subtle variation in vegetation spectra in the shortwave infrared can directly indicate biochemical constituents and be used to quantify them. Phenolics are of lesser abundance compared to the major plant constituents but, nonetheless, have important plant functions and ecological significance. Additional research is needed to advance our understanding of the

  9. Time variations of narrow absorption lines in high resolution quasar spectra

    NASA Astrophysics Data System (ADS)

    Boissé, P.; Bergeron, J.; Prochaska, J. X.; Péroux, C.; York, D. G.

    2015-09-01

    Aims: We have searched for temporal variations of narrow absorption lines in high resolution quasar spectra. A sample of five distant sources were assembled, for which two spectra are available, either VLT/UVES or Keck/HIRES, which were taken several years apart. Methods: We first investigate under which conditions variations in absorption line profiles can be detected reliably from high resolution spectra and discuss the implications of changes in terms of small-scale structure within the intervening gas or intrinsic origin. The targets selected allow us to investigate the time behaviour of a broad variety of absorption line systems by sampling diverse environments: the vicinity of active nuclei, galaxy halos, molecular-rich galaxy disks associated with damped Lyα systems, as well as neutral gas within our own Galaxy. Results: Intervening absorption lines from Mg ii, Fe ii, or proxy species with lines of lower opacity tracing the same kind of (moderately ionised) gas appear in general to be remarkably stable (1σ upper limits as low as 10% for some components on scales in the range 10-100 au), even for systems at zabs ≈ ze. Marginal variations are observed for Mg ii lines towards PKS 1229-021 at zabs = 0.83032; however, we detect no systems that display any change as large as those reported in low resolution SDSS spectra. The lack of clear variations for low β Mg ii systems does not support the existence of a specific population of absorbers made of swept-up gas towards blazars. In neutral or diffuse molecular media, clear changes are seen for Galactic Na i lines towards PKS 1229-02 (decrease in N by a factor of four for one of the five components over 9.7 yr), corresponding to structure on a scale of about 35 au, in good agreement with known properties of the Galactic interstellar medium. Tentative variations are detected for H2J = 3 lines towards FBQS J2340-0053 at zabs = 2.05454 (≃35% change in column density, N, over 0.7 yr in the rest frame), suggesting

  10. The Mid-Infrared Absorption Spectra of Neutral PAHs in Dense Interstellar Clouds

    NASA Technical Reports Server (NTRS)

    Bernstein, M. P.; Sandford, S. A.; Allamandola, L. J.

    2005-01-01

    Polycyclic aromatic hydrocarbons (PAHs) are common throughout the universe and are expected to be present in dense interstellar clouds. In these environments, some P.4Hs may be present in the gas phase, but most should be frozen into ice mantles or adsorbed onto dust grains and their spectral features are expected to be seen in absorption. Here we extend our previous work on the infrared spectral properties of the small PAH naphthalene (C10H8) in several media to include the full mid-infrared laboratory spectra of 11 other PAHs and related aromatic species frozen in H2O ices. These include the molecules 1,2-dihydronaphthalene, anthracene, 9,1O-dihydroanthracene, phenanthrene, pyrene, benzo[e]pyrene, perylene, benzo(k)fluoranthene, pentacene, benzo[ghi]perylene, and coronene. These results demonstrate that PAHs and related molecules, as a class, show the same spectral behaviors as naphthalene when incorporated into H2O-rich matrices. When compared to the spectra of these same molecules isolated in inert matrices (e.g., Ar or N2), the absorption bands produced when they are frozen in H2O matrices are broader (factors of 3-10), show small position shifts in either direction (usually < 4/cm, always < 10/cm), and show variable changes in relative band strengths (typically factors of 1-3). There is no evidence of systematic increases or decreases in the absolute strengths of the bands of these molecules when they are incorporated in H2O matrices. In H2O-rich ices, their absorption bands are relatively insensitive to concentration over the range of 10 < H2O/PAH < 200): The absorption bands of these molecules are also insensitive to temperature over the 10 K < T < 125 K range, although the spectra can show dramatic changes as the ices are warmed through the temperature range in which amorphous H2O ice converts to its cubic and hexagonal crystalline forms (T > 125 Kj. Given the small observed band shifts cause by H2O, the current database of spectra from Ar matrix

  11. Infrared band absorptance correlations and applications to nongray radiation. [mathematical models of absorption spectra for nongray atmospheres in order to study air pollution

    NASA Technical Reports Server (NTRS)

    Tiwari, S. N.; Manian, S. V. S.

    1976-01-01

    Various mathematical models for infrared radiation absorption spectra for atmospheric gases are reviewed, and continuous correlations for the total absorptance of a wide band are presented. Different band absorptance correlations were employed in two physically realistic problems (radiative transfer in gases with internal heat source, and heat transfer in laminar flow of absorbing-emitting gases between parallel plates) to study their influence on final radiative transfer results. This information will be applied to the study of atmospheric pollutants by infrared radiation measurement.

  12. Novel xenon calibration scheme for two-photon absorption laser induced fluorescence of hydrogen

    NASA Astrophysics Data System (ADS)

    Elliott, Drew; Scime, Earl; Short, Zachary

    2016-11-01

    Two photon absorption laser induced fluorescence (TALIF) measurements of neutral hydrogen and its isotopes are typically calibrated by performing TALIF measurements on krypton with the same diagnostic system and using the known ratio of the absorption cross sections [K. Niemi et al., J. Phys. D 34, 2330 (2001)]. Here we present the measurements of a new calibration method based on a ground state xenon scheme for which the fluorescent emission wavelength is nearly identical to that of hydrogen, thereby eliminating chromatic effects in the collection optics and simplifying detector calibration. We determine that the ratio of the TALIF cross sections of xenon and hydrogen is 0.024 ± 0.001.

  13. Effect of solvent on absorption spectra of all-trans-{beta}-carotene under high pressure

    SciTech Connect

    Liu, W. L.; Zheng, Z. R.; Liu, Z. G.; Zhu, R. B.; Wu, W. Z.; Li, A. H.; Yang, Y. Q.; Dai, Z. F.; Su, W. H.

    2008-03-28

    The absorption spectra of all-trans-{beta}-carotene in n-hexane and carbon disulfide (CS{sub 2}) solutions are measured under high pressure at ambient temperature. The common redshift and broadening in the spectra are observed. Simulation of the absorption spectra was performed by using the time-domain formula of the stochastic model. The pressure dependence of the 0-0 band wavenumber is in agreement with the Bayliss theory at pressure higher than 0.2 GPa. The deviation of the linearity at lower pressure is ascribed to the reorientation of the solvent molecules. Both the redshift and broadening are stronger in CS{sub 2} than that in n-hexane because of the more sensitive pressure dependence of dispersive interactions in CS{sub 2} solution. The effect of pressure on the transition moment is explained with the aid of a simple model involving the relative dimension, location, and orientation of the solute and solvent molecules. The implication of these results for light-harvesting functions of carotenoids in photosynthesis is also discussed.

  14. The effect of ionization on the infrared absorption spectra of PAHs: A preliminary report

    NASA Technical Reports Server (NTRS)

    Defrees, Doug J.; Miller, M. D.

    1989-01-01

    The emission lines observed in many interstellar IR sources at 3.28, 6.2, 7.7, 8.7, and 11.3 microns are theorized to originate from polycyclic aromatic hydrocarbons (PAHs). These assignments are based on analyses of lab IR spectra of neutral PAHs. However, it is likely that in the interstellar medium that PAHs are ionized, i.e., are positively charged. Besides, as pointed out by Allamandola et al., although the IR emission band spectrum resembles what one might expect from a mixture of PAHs, it does not match in details such as frequency, band profile, or relative intensities predicted from the absorption spectra of any known PAH molecule. One source of more information to test the PAH theory is ab initio molecular orbital theory. It can be used to compute, from first principles, the geometries, vibrational frequencies, and vibrational intensities for model PAH compounds which are difficult to study in the lab. The Gaussian 86 computer program was used to determine the effect of ionization on the infrared absorption spectra of several small PAHs: naphthalene and anthracene. A preliminary report is presented of the results of these calculations.

  15. Measurability of Kinetic Temperature from Metal Absorption-Line Spectra Formed in Chaotic Media

    NASA Astrophysics Data System (ADS)

    Levshakov, Sergei A.; Takahara, Fumio; Agafonova, Irina I.

    1999-06-01

    We present a new method for recovering the kinetic temperature of the intervening diffuse gas to an accuracy of 10%. The method is based on the comparison of unsaturated absorption-line profiles of two species with different atomic weights. The species are assumed to have the same temperature and bulk motion within the absorbing region. The computational technique involves the Fourier transform of the absorption profiles and the consequent entropy-regularized χ2-minimization (ERM) to estimate the model parameters. The procedure is tested using synthetic spectra of C+, Si+, and Fe+ ions. The comparison with the standard Voigt fitting analysis is performed, and it is shown that the Voigt deconvolution of the complex absorption-line profiles may result in estimated temperatures that are not physical. We also successfully analyze Keck telescope spectra of C II λ1334 and Si II λ1260 lines observed at the redshift z=3.572 toward the quasar Q1937-1009 by Tytler et al. Based in part on data obtained at the W. M. Keck Observatory, which is jointly operated by the University of California and the California Institute of Technology.

  16. Effects of Spectralon absorption on reflectance spectra of typical planetary surface analog materials.

    PubMed

    Zhang, Hao; Yang, Yazhou; Jin, Weidong; Liu, Chujian; Hsu, Weibiao

    2014-09-01

    Acquiring accurate visible and near-infrared (VisNIR) reflectance values of atmosphereless celestial bodies is very important in inferring the physical and geological properties of their surficial materials. When a calibration target with inherent non-trivial absorption features is used, the calibrated reflectance would essentially always contain spurious spectral features and the spectroscopic data may easily be misinterpreted if the artifact is not properly taken care of. We demonstrate with laboratory reflectance measurements that the VisNIR spectra of three typical planetary surface analog materials, lunar simulant JSC-1A, olivine and pyroxene grains, have an artificial peak at 2.1 µm when Spectralon-type plaque made of polytetrafluoroethylene is used as the calibration target in the NIR region. The degree of severity of this artifact is dependent on the strength of the 2.0 µm absorption feature of the mineral. Empirical methods are proposed to remove this artifact to bring the spectra close to that calibrated by a gold mirror which does not have any conspicuous absorption features in the NIR region. The correction methods may be applied to reflectance data acquired by the VisNIR imaging spectrometer onboard the Yutu Rover of the Chinese Chang'E 3 lunar mission which employed an onboard Spectralon-type calibration target. PMID:25321507

  17. Effects of Spectralon absorption on reflectance spectra of typical planetary surface analog materials.

    PubMed

    Zhang, Hao; Yang, Yazhou; Jin, Weidong; Liu, Chujian; Hsu, Weibiao

    2014-09-01

    Acquiring accurate visible and near-infrared (VisNIR) reflectance values of atmosphereless celestial bodies is very important in inferring the physical and geological properties of their surficial materials. When a calibration target with inherent non-trivial absorption features is used, the calibrated reflectance would essentially always contain spurious spectral features and the spectroscopic data may easily be misinterpreted if the artifact is not properly taken care of. We demonstrate with laboratory reflectance measurements that the VisNIR spectra of three typical planetary surface analog materials, lunar simulant JSC-1A, olivine and pyroxene grains, have an artificial peak at 2.1 µm when Spectralon-type plaque made of polytetrafluoroethylene is used as the calibration target in the NIR region. The degree of severity of this artifact is dependent on the strength of the 2.0 µm absorption feature of the mineral. Empirical methods are proposed to remove this artifact to bring the spectra close to that calibrated by a gold mirror which does not have any conspicuous absorption features in the NIR region. The correction methods may be applied to reflectance data acquired by the VisNIR imaging spectrometer onboard the Yutu Rover of the Chinese Chang'E 3 lunar mission which employed an onboard Spectralon-type calibration target.

  18. The synchronous fluorescence spectra character of hypocrellin B with type I collagen under irradiation

    NASA Astrophysics Data System (ADS)

    Zhang, Jucheng; Yan, Heping; Yang, Mengting; Feng, Yongzhen; Huang, Yun; Li, Lingmei; Liu, Wei

    2014-09-01

    The synchronous fluorescence (SF) technique can provide some useful information with the endogenous fluorophores in complex systems. The SF technique has been used in the characterization of the type I collagen in PBS solution (pH=7.4) and the photo-reaction of hypocrellin B (HB) with type I collagen in solution irradiation with the 475 nm light under saturated by oxygen, air and nitrogen respectively. The SF spectra show the peaks attribute to tyrosine residues (275 nm) and pyridinoline cross-link (325 nm) in collagen. The photo-induced reaction with HB causing the fluorescence quenching but no wavelength shift, this suggests the photo-reaction don't changing the microenvironment of PYD cross-link. The fluorescence quenching rate is faster than others when the solution saturated by oxygen. The results imply that the photo-induced reaction is oxygen dependence.

  19. Measurement of Gas and Aerosol Phase Absorption Spectra across the Visible and Near-IR Using Supercontinuum Photoacoustic Spectroscopy.

    PubMed

    Radney, James G; Zangmeister, Christopher D

    2015-07-21

    We demonstrate a method to measure the absorption spectra of gas and aerosol species across the visible and near-IR (500 to 840 nm) using a photoacoustic (PA) spectrometer and a pulsed supercontinuum laser source. Measurements of gas phase absorption spectra were demonstrated using H2O(g) as a function of relative humidity (RH). The measured absorption intensities and peak shapes were able to be quantified and compared to spectra calculated using the 2012 High Resolution Transmission (HITRAN2012) database. Size and mass selected nigrosin aerosol was used to measure absorption spectra across the visible and near-IR. Spectra were measured as a function of aerosol size/mass and show good agreement to Mie theory calculations. Lastly, we measured the broadband absorption spectrum of flame generated soot aerosol at 5% and 70% RH. For the high RH case, we are able to quantifiably separate the soot and water absorption contributions. For soot, we observe an enhancement in the mass specific absorption cross section ranging from 1.5 at 500 nm (p < 0.01) to 1.2 at 840 nm (p < 0.2) and a concomitant increase in the absorption Ångström exponent from 1.2 ± 0.4 (5% RH) to 1.6 ± 0.3 (70% RH). PMID:26098142

  20. Note: Measurement of saturable absorption by intense vacuum ultraviolet free electron laser using fluorescent material

    SciTech Connect

    Inubushi, Y.; Kumagai, T.; Morimoto, S.; Tanaka, T.; Kodama, R.; Yoneda, H.; Higashiya, A.; Ishikawa, T.; Nagasono, M.; Tono, K.; Yabashi, M.; Kimura, H.; Ohashi, H.; Togashi, T.; Sato, F.; Yamaguchi, Y.

    2010-03-15

    Advances in free electron lasers (FELs) which generate high energy photons are expected to open novel nonlinear optics in the x-ray and vacuum ultraviolet (VUV) regions. In this paper, we report a new method for performing VUV-FEL focusing experiments. A VUV-FEL was focused with Kirkpatrick-Baez optics on a multilayer target, which contains fused silica as a fluorescent material. By measuring the fluorescence, a 5.6x4.9 {mu}m{sup 2} focal spot was observed in situ. Fluorescence was used to measure the saturable absorption of VUV pulses in the tin layer. The transmission increases nonlinearly higher with increasing laser intensity.

  1. First-principles calculation of ground and excited-state absorption spectra of ruby and alexandrite considering lattice relaxation

    NASA Astrophysics Data System (ADS)

    Watanabe, Shinta; Sasaki, Tomomi; Taniguchi, Rie; Ishii, Takugo; Ogasawara, Kazuyoshi

    2009-02-01

    We performed first-principles calculations of multiplet structures and the corresponding ground-state absorption and excited-state absorption spectra for ruby (Cr3+:α-Al2O3) and alexandrite (Cr3+:BeAl2O4) which included lattice relaxation. The lattice relaxation was estimated using the first-principles total energy and molecular-dynamics method of the CASTEP code. The multiplet structure and absorption spectra were calculated using the configuration-interaction method based on density-functional calculations. For both ruby and alexandrite, the theoretical absorption spectra, which were already in reasonable agreement with experimental spectra, were further improved by consideration of lattice relaxation. In the case of ruby, the peak positions and peak intensities were improved through the use of models with relaxations of 11 or more atoms. For alexandrite, the polarization dependence of the U band was significantly improved, even by a model with a relaxation of only seven atoms.

  2. Small fluorescence-activating and absorption-shifting tag for tunable protein imaging in vivo

    PubMed Central

    Plamont, Marie-Aude; Billon-Denis, Emmanuelle; Maurin, Sylvie; Gauron, Carole; Pimenta, Frederico M.; Specht, Christian G.; Shi, Jian; Quérard, Jérôme; Pan, Buyan; Rossignol, Julien; Moncoq, Karine; Morellet, Nelly; Volovitch, Michel; Lescop, Ewen; Chen, Yong; Triller, Antoine; Vriz, Sophie; Le Saux, Thomas; Jullien, Ludovic; Gautier, Arnaud

    2016-01-01

    This paper presents Yellow Fluorescence-Activating and absorption-Shifting Tag (Y-FAST), a small monomeric protein tag, half as large as the green fluorescent protein, enabling fluorescent labeling of proteins in a reversible and specific manner through the reversible binding and activation of a cell-permeant and nontoxic fluorogenic ligand (a so-called fluorogen). A unique fluorogen activation mechanism based on two spectroscopic changes, increase of fluorescence quantum yield and absorption red shift, provides high labeling selectivity. Y-FAST was engineered from the 14-kDa photoactive yellow protein by directed evolution using yeast display and fluorescence-activated cell sorting. Y-FAST is as bright as common fluorescent proteins, exhibits good photostability, and allows the efficient labeling of proteins in various organelles and hosts. Upon fluorogen binding, fluorescence appears instantaneously, allowing monitoring of rapid processes in near real time. Y-FAST distinguishes itself from other tagging systems because the fluorogen binding is highly dynamic and fully reversible, which enables rapid labeling and unlabeling of proteins by addition and withdrawal of the fluorogen, opening new exciting prospects for the development of multiplexing imaging protocols based on sequential labeling. PMID:26711992

  3. Small fluorescence-activating and absorption-shifting tag for tunable protein imaging in vivo.

    PubMed

    Plamont, Marie-Aude; Billon-Denis, Emmanuelle; Maurin, Sylvie; Gauron, Carole; Pimenta, Frederico M; Specht, Christian G; Shi, Jian; Quérard, Jérôme; Pan, Buyan; Rossignol, Julien; Moncoq, Karine; Morellet, Nelly; Volovitch, Michel; Lescop, Ewen; Chen, Yong; Triller, Antoine; Vriz, Sophie; Le Saux, Thomas; Jullien, Ludovic; Gautier, Arnaud

    2016-01-19

    This paper presents Yellow Fluorescence-Activating and absorption-Shifting Tag (Y-FAST), a small monomeric protein tag, half as large as the green fluorescent protein, enabling fluorescent labeling of proteins in a reversible and specific manner through the reversible binding and activation of a cell-permeant and nontoxic fluorogenic ligand (a so-called fluorogen). A unique fluorogen activation mechanism based on two spectroscopic changes, increase of fluorescence quantum yield and absorption red shift, provides high labeling selectivity. Y-FAST was engineered from the 14-kDa photoactive yellow protein by directed evolution using yeast display and fluorescence-activated cell sorting. Y-FAST is as bright as common fluorescent proteins, exhibits good photostability, and allows the efficient labeling of proteins in various organelles and hosts. Upon fluorogen binding, fluorescence appears instantaneously, allowing monitoring of rapid processes in near real time. Y-FAST distinguishes itself from other tagging systems because the fluorogen binding is highly dynamic and fully reversible, which enables rapid labeling and unlabeling of proteins by addition and withdrawal of the fluorogen, opening new exciting prospects for the development of multiplexing imaging protocols based on sequential labeling. PMID:26711992

  4. Absorption features in the 5-8 micron spectra of protostars

    NASA Technical Reports Server (NTRS)

    Tielens, A. G. G. M.; Allamandola, L. J.; Bregman, J.; Goebel, J.; Witteborn, F. C.; Dhendecourt, L. B.

    1984-01-01

    High signal-to-noise ratio spectra in the range of 5-8 microns of four sources embedded in molecular clouds are examined using low-temperature laboratory measurements of the 5-8-micron spectra of simple molecules and their mixtures. The absorption, apparent in all four sources, is characterized by highly distinct features ranging from two relatively narrow bands at 6.0 and 6.8 microns in W33A to a broad, shallow, and partially structured feature extending from 5.2 to 7.8 microns in Mon R2-IRS2, BN, and NGC2264. The first feature (W33A) is explained by the OH bending mode in H2O and the CH deformation modes in saturated hydrocarbons; while the second feature (Mon R2-IRS2-type) is explained by the presence of a mixture of saturated and unsaturated hydrocarbons possibly containing strongly electronegative groups.

  5. Ultrafast optical nonlinearity, electronic absorption, vibrational spectra and solvent effect studies of ninhydrin

    NASA Astrophysics Data System (ADS)

    Sajan, D.; Devi, T. Uma; Safakath, K.; Philip, Reji; Němec, Ivan; Karabacak, M.

    2013-05-01

    FT-IR, FT-Raman and UV-Vis spectra of the nonlinear optical molecule ninhydrin have been recorded and analyzed. The equilibrium geometry, bonding features, and harmonic vibrational wavenumbers have been investigated with the help of B3LYP density functional theory method. A detailed interpretation of the vibrational spectra is carried out with the aid of normal coordinate analysis following the scaled quantum mechanical force field methodology. Solvent effects have been calculated using time-dependent density functional theory in combination with the polarized continuum model. Natural bond orbital analysis confirms the occurrence of strong intermolecular hydrogen bonding in the molecule. Employing the open-aperture z-scan technique, nonlinear optical absorption of the sample has been studied in the ultrafast and short-pulse excitation regimes, using 100 fs and 5 ns laser pulses respectively. It is found that ninhydrin exhibits optical limiting for both excitations, indicating potential photonic applications.

  6. Pressure dependence of Hexanitrostilbene Raman/ electronic absorption spectra to validate DFT EOS

    NASA Astrophysics Data System (ADS)

    Farrow, Darcie; Alam, Kathleen; Martin, Laura; Fan, Hongyou; Kay, Jeffrey; Wixom, Ryan

    2015-06-01

    Due to its thermal stability and low vapor pressure, Hexanitrostilbene (HNS) is often used in high-temperature or vacuum applications as a detonator explosive or in mild detonating fuse. Toward improving the accuracy of the equation of state used in hydrodynamic simulations of the performance of HNS, we have measured the Raman and electronic absorption spectra of this material under static pressure in a diamond anvil cell. Density functional theory calculations were used to simulate the pressure dependence of the Raman/Electronic spectra along the Hugoniot and 300K isotherm for comparison and to aid in interpreting the data. We will discuss changes in the electronic structure of HNS under pressure, validation of a DFT predicted equation of state (EOS), and using this data as a basis for understanding future pulsed Raman measurements on dynamically compressed HNS samples.

  7. Solvatochromic behavior of the electronic absorption spectra of gallic acid and some of its azo derivatives

    NASA Astrophysics Data System (ADS)

    Masoud, Mamdouh S.; Hagagg, Sawsan S.; Ali, Alaa E.; Nasr, Nessma M.

    The electronic absorption spectra of gallic acid and its azo derivatives have been studied in various solvents of different polarities. Multiple regression techniques were applied to calculate the regression and correlation coefficients based on an equation that relates the wavenumbers of the absorption band maxima (υmax-) to the solvent parameters; refractive index (n), dielectric constant (D), empirical Kamlet-Taft solvent parameters, π*(dipolarity/polarizability), α (solvent hydrogen-bond donor acidity) and β (solvent hydrogen-bond acceptor basicity). The fitting coefficient obtained from this analysis allows estimating the contribution of each type of interactions relative to total spectral shifts in solution. The dependence of υmax- on the solvent parameters indicates that the obtained bands are affected by specific and non-specific solute-solvent interactions.

  8. Solvatochromic behavior of the electronic absorption spectra of gallic acid and some of its azo derivatives.

    PubMed

    Masoud, Mamdouh S; Hagagg, Sawsan S; Ali, Alaa E; Nasr, Nessma M

    2012-08-01

    The electronic absorption spectra of gallic acid and its azo derivatives have been studied in various solvents of different polarities. Multiple regression techniques were applied to calculate the regression and correlation coefficients based on an equation that relates the wavenumbers of the absorption band maxima (υ(max)(-)) to the solvent parameters; refractive index (n), dielectric constant (D), empirical Kamlet-Taft solvent parameters, π*(dipolarity/polarizability), α (solvent hydrogen-bond donor acidity) and β (solvent hydrogen-bond acceptor basicity). The fitting coefficient obtained from this analysis allows estimating the contribution of each type of interactions relative to total spectral shifts in solution. The dependence of υ(max)(-) on the solvent parameters indicates that the obtained bands are affected by specific and non-specific solute-solvent interactions.

  9. Index of Refraction and Absorption Coefficient Spectra of Paratellurite in the Terahertz Region

    NASA Astrophysics Data System (ADS)

    Unferdorben, Márta; Buzády, Andrea; Hebling, János; Kiss, Krisztián; Hajdara, Ivett; Kovács, László; Péter, Ágnes; Pálfalvi, László

    2016-07-01

    Index of refraction and absorption coefficient spectra of pure paratellurite (α-TeO2) crystal as a potential material for terahertz (THz) applications were determined in the 0.25-2 THz frequency range at room temperature by THz time domain spectroscopy (THz-TDS). The investigation was performed with beam polarization both parallel (extraordinary polarization) and perpendicular (ordinary polarization) to the optical axis [001] of the crystal. Similarly to the visible spectral range, positive birefringence was observed in the THz range as well. It was shown that the values of the refractive index for extraordinary polarization are higher and show significantly larger dispersion than for the ordinary one. The absorption coefficient values are also larger for extraordinary polarization. The measured values were fitted by theoretical curves derived from the complex dielectric function containing independent terms of Lorentz oscillators due to phonon-polariton resonances. The results are compared with earlier publications, and the observed significant discrepancies are discussed.

  10. Effects of domain size on x-ray absorption spectra of boron nitride doped graphenes

    NASA Astrophysics Data System (ADS)

    Li, Xin; Hua, Weijie; Wang, Bo-Yao; Pong, Way-Faung; Glans, Per-Anders; Guo, Jinghua; Luo, Yi

    2016-08-01

    Doping is an efficient way to open the zero band gap of graphene. The control of the dopant domain size allows us to tailor the electronic structure and the properties of the graphene. We have studied the electronic structure of boron nitride doped graphenes with different domain sizes by simulating their near-edge X-ray absorption fine structure (NEXAFS) spectra at the N K-edge. Six different doping configurations (five quantum dot type and one phase-separated zigzag-edged type) were chosen, and N K-edge NEXAFS spectra were calculated with large truncated cluster models by using the density functional theory with hybrid functional and the equivalent core hole approximation. The opening of the band gap as a function of the domain size is revealed. We found that nitrogens in the dopant boundary contribute a weaker, red-shifted π* peak in the spectra as compared to those in the dopant domain center. The shift is related to the fact that these interfacial nitrogens dominate the lowest conduction band of the system. Upon increasing the domain size, the ratio of interfacial atom decreases, which leads to a blue shift of the π* peak in the total NEXAFS spectra. The spectral evolution agrees well with experiments measured at different BN-dopant concentrations and approaches to that of a pristine h-BN sheet.

  11. Appraisal of Surface Hopping as a Tool for Modeling Condensed Phase Linear Absorption Spectra.

    PubMed

    Petit, Andrew S; Subotnik, Joseph E

    2015-09-01

    Whereas surface hopping is usually used to study populations and mean-field dynamics to study coherences, in two recent papers, we described a procedure for calculating dipole-dipole correlation functions (and therefore absorption spectra) directly from ensembles of surface hopping trajectories. We previously applied this method to a handful of one-dimensional model problems intended to mimic the gas phase. In this article, we now benchmark this new procedure on a set of multidimensional model problems intended to mimic the condensed phase and compare our results against other standard semiclassical methods. By comparison, we demonstrate that methods that include only dynamical information from one PES (the standard Kubo approaches) exhibit large discrepancies with the results of exact quantum dynamics. Furthermore, for model problems with nonadiabatic excited state dynamics but no quantized vibrational structure in the spectra, our surface hopping approach performs comparably to using Ehrenfest dynamics to calculate the electronic coherences. That being said, however, when quantized vibrational structures are present in the spectra but the electronic states are uncoupled, performing the dynamics on the mean PES still outperforms our present method. These benchmark results should influence future studies that use ensembles of independent semiclassical trajectories to model linear as well as multidimensional spectra in the condensed phase.

  12. Solvent effects on the S0 →S2 absorption spectra of β-carotene

    NASA Astrophysics Data System (ADS)

    Liu, Wei-Long; Wang, De-Min; Zheng, Zhi-Ren; Li, Ai-Hua; Su, Wen-Hui

    2010-01-01

    Absorption spectra of β-carotene in 31 solvents are measured in ambient conditions. Solvent effects on the 0-0 band energy, the bandwidth, and the transition moment of the S0 → S2 transition are analysed. The discrepancies between published results of the solvent effects on the 0-0 band energy are explained by taking into account microscopic solute-solvent interactions. The contributions of polarity and polarizability of solvents to 0-0 band energy and bandwidth are quantitatively distinguished. The 0-0 transition energy of the S2 state at the gas phase is predicted to locate between 23000 and 23600 cm-1.

  13. Electronic properties and absorption spectra of ZnSnP2 using mBJ potential

    NASA Astrophysics Data System (ADS)

    Joshi, Ritu; Ahuja, B. L.

    2015-06-01

    We present the energy bands and density of states of ZnSnP2 using full potential linearized augmented plane wave method with modified Becke Johnson potential. It is found that this compound has a direct band gap of about 2.01 eV at Γ point, which originates from the energy difference between P-3p and Sn-5s states. In addition, we have also calculated absorption spectra in the solar energy range and compared it with that of bulk Si to explore the applicability of ZnSnP2 in photovoltaic and optoelectronic devices.

  14. Decay heat and anti-neutrino energy spectra in fission fragments from total absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Rykaczewski, Krzysztof

    2015-10-01

    Decay studies of over forty 238U fission products have been studied using ORNL's Modular Total Absorption Spectrometer. The results are showing increased decay heat values, by 10% to 50%, and the energy spectra of anti-neutrinos shifted towards lower energies. The latter effect is resulting in a reduced number of anti-neutrinos interacting with matter, often by tens of percent per fission product. The results for several studied nuclei will be presented and their impact on decay heat pattern in power reactors and reactor anti-neutrino physics will be discussed.

  15. IR absorption and surface-enhanced Raman spectra of the isoquinoline alkaloid berberine

    NASA Astrophysics Data System (ADS)

    Strekal', N. D.; Motevich, I. G.; Nowicky, J. W.; Maskevich, S. A.

    2007-01-01

    We present the IR absorption and surface-enhanced Raman scattering (SERS) spectra of the isoquinoline alkaloid berberine adsorbed on a silver hydrosol and on the surface of a silver electrode for different potentials. Based on quantum chemical calculations, for the first time we have assigned the vibrations in the berberine molecule according to vibrational mode. The effect of the potential of the silver electrode on the geometry of sorption of the molecule on the surface is considered, assuming a short-range mechanism for enhancement of Raman scattering.

  16. On Different Absorption Components in the X-ray Spectra of the Intermediate Polar Systems

    NASA Astrophysics Data System (ADS)

    Balman, S.; Okcu, B.

    2014-07-01

    We present orbital phase-resolved spectroscopy of the Intermediate polars (IP) AO Psc, HT Cam, V1223 Sgr and XSS J0056+4548 using the XMM-Newton EPIC pn data. We detect increase of absorption by neutral hydrogen column density N_{H} during the phases corresponding to the orbital minima in a range ˜ (1.0-2.0)× 10^{22} cm^{-2}. AO Psc indicates spectral hardening in the soft plasma emission component. HT Cam, reveals an increase of N_{H} at the orbital minimum from 0.05× 10^{22} cm^{-2} to 0.13× 10^{22} cm^{-2}. These high N_{H} values are most likely a result of absorption by the bulge material at the accretion impact zone. We discuss implications of this interms of warmabsorbers in IPs and bulge temperatures. The four IPs reveal a second high absorption component that is constant over the orbital phase in a range (5.0-11.0)× 10^{22} cm^{-2}. We attribute this component to the accretion column/curtain. These results are in accordance with the orbital phase-resolved analysis presented in Pekon & Balman (2011) for EX Hya and (2012) for FO Aqr. We strongly suggest that absorption by the bulge at the accretion impact zone is a distinct component in the IP X-ray spectra.

  17. Galactic Soft X-ray Emission Revealed with Spectroscopic Study of Absorption and Emission Spectra

    NASA Astrophysics Data System (ADS)

    Yamasaki, Noriko Y.; Mitsuda, K.; Takei, Y.; Hagihara, T.; Yoshino, T.; Wang, Q. D.; Yao, Y.; McCammon, D.

    2010-03-01

    Spectroscopic study of Oxygen emission/absorption lines is a new tool to investigate the nature of the soft X-ray background. We investigated the emission spectra of 14 fields obtained by Suzaku, and detected OVII and OVIII lines separately. There is an almost isotropic OVII line emission with 2 LU intensity. As the attenuation length in the Galactic plane for that energy is short, that OVII emission should arise within 300 pc of our neighborhood. In comparison with the estimated emission measure for the local bubble, the most plausible origin of this component is the solar wind charge exchange with local interstellar materials. Another component presented from the correlation between the OVII and OVIII line intensity is a thermal emission with an apparent temperature of 0.2 keV with a field-to-field fluctuation of 10% in temperature, while the intensity varies about a factor of 4. By the combination analysis of the emission and the absorption spectra, we can investigate the density and the scale length of intervening plasma separately. We analyzed the Chanrdra grating spectra of LMC X-3 and PKS 2155-304, and emission spectra toward the line of sight by Suzaku. In both cases, the combined analysis showed that the hot plasma is not iso-thermal nor uniform. Assuming an exponential disk distribution, the thickness of the disk is as large as a few kpc. It suggests that there is a thick hot disk or hot halo surrounding our Galaxy, which is similar to X-ray hot haloes around several spiral galaxies.

  18. Modeling the absorption spectra of Er3+ and Yb3+ in a phosphate glass

    NASA Astrophysics Data System (ADS)

    Gruber, John B.; Sardar, Dhiraj K.; Zandi, Bahram; Hutchinson, J. Andrew; Trussell, C. Ward

    2003-10-01

    Absorption spectra of Er3+ and Yb3+ ions, codopants in a phosphate glass, are reported at 8 K and at wavelengths between 350 and 1600 nm. Detailed structure appearing in the spectra, associated with individual multiplet states, 2S+1LJ, of Er3+(4f11) and Yb3+(4f13) is interpreted using a ligand-field coordination sphere model to characterize the microscopic environment surrounding the rare earth ions in multiple sites. Inhomogeneous broadening of the spectra is likely due to different configurations of PO4 tetrahedra clustered about a caged rare earth ion in the amorphous host. Similarity between the Er3+ spectrum in the glass and in the spectrum of single-crystal LiErP4O12, where Er3+ occupies sites of C2 symmetry, suggests that an averaged site symmetry of C2 is a reasonable approximation for Er3+ and Yb3+ ions in the phosphate glass. Calculated splitting of multiplet states by the ligand-field cluster model are compared with energy levels derived from the observed absorption peaks and well-defined shoulders. Inhomogeneous broadening of the spectra limit the precision in establishing the energy of the multiplet splittings, but the analysis is useful for modeling studies of the Er:Yb:phosphate glass as an eye-safe laser (1.53 μm). The splitting of the Yb3+(4f13)2FJ states is determined using parameters obtained from the Er3+ set by means of the three-parameter theory. No adjustments were made to the Yb3+ parameters that predict multiplet splittings in reasonable agreement with experimental data.

  19. Determination of phosphorus using high-resolution diphosphorus molecular absorption spectra produced in the graphite furnace

    NASA Astrophysics Data System (ADS)

    Huang, Mao Dong; Becker-Ross, Helmut; Okruss, Michael; Geisler, Sebastian; Florek, Stefan

    2016-01-01

    Molecular absorption of diphosphorus was produced in a graphite furnace and evaluated in view of its suitability for phosphorus determination. Measurements were performed with two different high-resolution continuum source absorption spectrometers. The first system is a newly in-house developed simultaneous broad-range spectrograph, which was mainly used for recording overview absorption spectra of P2 between 193 nm and 245 nm. The region covers the main part of the C 1Σu+ ← X 1Σg+ electronic transition and shows a complex structure with many vibrational bands, each consisting of a multitude of sharp rotational lines. With the help of molecular data available for P2, an assignment of the vibrational bands was possible and the rotational structure could be compared with simulated spectra. The second system is a commercial sequential continuum source spectrometer, which was used for the basic analytical measurements. The P2 rotational line at 204.205 nm was selected and systematically evaluated with regard to phosphorus determination. The conditions for P2 generation were optimized and it was found that the combination of a ZrC modified graphite tube and borate as a chemical modifier were essential for a good production of P2. Serious interferences were found in the case of nitrate and sulfuric acid, although the nitrate interference can be eliminated by a higher pyrolysis temperature. The reliability of the method was proved by analysis of certified samples. Using standard tubes, a characteristic mass of 10 ng and a limit of detection of 7 ng were found. The values could further be improved by a factor of ten using a miniaturized tube with an internal diameter of 2 mm. Compared to the conventional method based on the phosphorus absorption line at 213.618 nm, the advantages of using P2 are the gentle temperature conditions and the potential of performing a simultaneous multi-line evaluation to further improve the limit of detection.

  20. Determination of the in vivo redox potential using roGFP and fluorescence spectra obtained from one-wavelength excitation

    NASA Astrophysics Data System (ADS)

    Wierer, S.; Elgass, K.; Bieker, S.; Zentgraf, U.; Meixner, A. J.; Schleifenbaum, F.

    2011-02-01

    The analysis of molecular processes in living (plant) cells such as signal transduction, DNA replication, carbon metabolism and senescence has been revolutionized by the use of green fluorescent protein (GFP) and its variants as specific cellular markers. Many cell biological processes are accompanied by changes in the intracellular redox potential. To monitor the redox potential, a redox-sensitive mutant of GFP (roGFP) was created, which shows changes in its optical properties in response to changes in the redox state of its surrounding medium. For a quantitative analysis in living systems, it is essential to know the optical properties of roGFP in vitro. Therefore, we applied spectrally resolved fluorescence spectroscopy on purified roGFP exposed to different redox potentials to determine shifts in both the absorption and the emission spectra of roGFP. Based on these in vitro findings, we introduce a new approach using one-wavelength excitation to use roGFP for the in vivo analysis of cell biological processes. We demonstrate the ability this technique by investigating chloroplast-located Grx1-roGFP2 expressing Arabidopsis thaliana cells as example for dynamically moving intracellular compartments. This is not possible with the two-wavelength excitation technique established so far, which hampers a quantitative analysis of highly mobile samples due to the time delay between the two measurements and the consequential displacement of the investigated area.

  1. Absorption and fluorescence anisotropies of monoclinic crystals: the case of Nd:YCOB.

    PubMed

    Petit, Yannick; Boulanger, Benoît; Segonds, Patricia; Félix, Corinne; Ménaert, Bertrand; Zaccaro, Julien; Aka, Gérard

    2008-05-26

    We report for the first time measurements and modelization of the angular distributions of absorption and fluorescence in a monoclinic crystal. Studies on Nd:YCOB revealed specific topologies with ombilics. These new data upgrade the knowledge on low symmetry crystal optics.

  2. Optical imaging of non-fluorescent nanodiamonds in live cells using transient absorption microscopy.

    PubMed

    Chen, Tao; Lu, Feng; Streets, Aaron M; Fei, Peng; Quan, Junmin; Huang, Yanyi

    2013-06-01

    We directly observe non-fluorescent nanodiamonds in living cells using transient absorption microscopy. This label-free technology provides a novel modality to study the dynamic behavior of nanodiamonds inside the cells with intrinsic three-dimensional imaging capability. We apply this method to capture the cellular uptake of nanodiamonds under various conditions, confirming the endocytosis mechanism.

  3. Study of the Photodegradation Process of Vitamin E Acetate by Optical Absorption, Fluorescence, and Thermal Lens Spectroscopy

    NASA Astrophysics Data System (ADS)

    Tiburcio-Moreno, J. A.; Marcelín-Jiménez, G.; Leanos-Castaneda, O. L.; Yanez-Limon, J. M.; Alvarado-Gil, J. J.

    2012-11-01

    The stability of vitamin E acetate exposed to ultraviolet (UV) light was studied using three spectroscopic methods. An ethanol solution of vitamin E acetate was treated with either UVC light (254 nm) or UVA light (366 nm) during a period of 10 min followed by a study of UV-Vis optical absorption, then by fluorescence spectroscopy excitation by UV radiation at either 290 nm or 368 nm and, finally the solution was studied by thermal lens spectroscopy. Immediately, the same solution of vitamin E acetate was subjected to the UV irradiation process until completion of six periods of irradiation and measurements. UVC light treatment induced the appearance of a broad absorption band in the range of 310 nm to 440 nm with maximum absorbance at 368 nm, which progressively grew as the time of the exposure to UVC light increases. In contrast, UVA light treatment did not affect the absorption spectra of vitamin E acetate. Fluorescence spectra of the vitamin E acetate (without UV light treatment) showed no fluorescence when excited with 368 nm while exciting with 290 nm, an intense and broad emission band (300 nm to 440 nm) with a maximum at 340 nm appeared. When vitamin E acetate was treated with UVC light, this emission band progressively decreased as the time of the UVC light irradiation grew. No signal from UV-untreated vitamin E acetate could be detected by the thermal lens method. Interestingly, as the time of the UVC light treatment increased, the thermal lens signal progressively grew. Additional experiments performed to monitor the time evolution of the process during continuous UVC treatment of the vitamin E acetate using thermal lens spectroscopy exhibited a progressive increase of the thermal lens signal reaching a plateau at about 8000 s. This study shows that the vitamin E acetate is stable when it is irradiated with UVA light, while the irradiation with UVC light induces the formation of photodegradation products. Interestingly, this photodegradation process using

  4. Identifying Student and Teacher Difficulties in Interpreting Atomic Spectra Using a Quantum Model of Emission and Absorption of Radiation

    ERIC Educational Resources Information Center

    Savall-Alemany, Francisco; Domènech-Blanco, Josep Lluís; Guisasola, Jenaro; Martínez-Torregrosa, Joaquín

    2016-01-01

    Our study sets out to identify the difficulties that high school students, teachers, and university students encounter when trying to explain atomic spectra. To do so, we identify the key concepts that any quantum model for the emission and absorption of electromagnetic radiation must include to account for the gas spectra and we then design two…

  5. Optical and structural properties of plasma-treated Cordyceps bassiana spores as studied by circular dichroism, absorption, and fluorescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Lee, Geon Joon; Sim, Geon Bo; Choi, Eun Ha; Kwon, Young-Wan; Kim, Jun Young; Jang, Siun; Kim, Seong Hwan

    2015-01-01

    To understand the killing mechanism of fungal spores by plasma treatment, the optical, structural, and biological properties of the insect pathogenic fungus Cordyceps bassiana spores were studied. A nonthermal atmospheric-pressure plasma jet (APPJ) was used to treat the spores in aqueous solution. Optical emission spectra of the APPJ acquired in air indicated emission peaks corresponding to hydroxyl radicals and atomic oxygen. When the APPJ entered the aqueous solution, additional reactive species were derived from the interaction of plasma radicals with the aqueous solution. Fluorescence and absorption spectroscopy confirmed the generation of hydroxyl radicals and hydrogen peroxide in the plasma-activated water (PAW). Spore counting showed that plasma treatment significantly reduced spore viability. Absorption spectroscopy, circular dichroism (CD) spectroscopy, and agarose gel electrophoresis of the DNA extracted from plasma-treated spores showed a reduction in spore DNA content. The magnitude of the dip in the CD spectrum was lower in the plasma-treated spores than in the control, indicating that plasma treatment causes structural modifications and/or damage to cellular components. Tryptophan fluorescence intensity was lower in the plasma-treated spores than in the control, suggesting that plasma treatment modified cell wall proteins. Changes in spore viability and DNA content were attributed to structural modification of the cell wall by reactive species coming from the APPJ and the PAW. Our results provided evidence that the plasma radicals and the derived reactive species play critical roles in fungal spore inactivation.

  6. Optical and structural properties of plasma-treated Cordyceps bassiana spores as studied by circular dichroism, absorption, and fluorescence spectroscopy

    SciTech Connect

    Lee, Geon Joon Sim, Geon Bo; Choi, Eun Ha; Kim, Jun Young; Jang, Siun; Kim, Seong Hwan

    2015-01-14

    To understand the killing mechanism of fungal spores by plasma treatment, the optical, structural, and biological properties of the insect pathogenic fungus Cordyceps bassiana spores were studied. A nonthermal atmospheric-pressure plasma jet (APPJ) was used to treat the spores in aqueous solution. Optical emission spectra of the APPJ acquired in air indicated emission peaks corresponding to hydroxyl radicals and atomic oxygen. When the APPJ entered the aqueous solution, additional reactive species were derived from the interaction of plasma radicals with the aqueous solution. Fluorescence and absorption spectroscopy confirmed the generation of hydroxyl radicals and hydrogen peroxide in the plasma-activated water (PAW). Spore counting showed that plasma treatment significantly reduced spore viability. Absorption spectroscopy, circular dichroism (CD) spectroscopy, and agarose gel electrophoresis of the DNA extracted from plasma-treated spores showed a reduction in spore DNA content. The magnitude of the dip in the CD spectrum was lower in the plasma-treated spores than in the control, indicating that plasma treatment causes structural modifications and/or damage to cellular components. Tryptophan fluorescence intensity was lower in the plasma-treated spores than in the control, suggesting that plasma treatment modified cell wall proteins. Changes in spore viability and DNA content were attributed to structural modification of the cell wall by reactive species coming from the APPJ and the PAW. Our results provided evidence that the plasma radicals and the derived reactive species play critical roles in fungal spore inactivation.

  7. [Study on the deteriorating course of fresh milk by laser-induced fluorescence spectra].

    PubMed

    Liu, J; Yu, C Q; Li, J Z; Yan, J X

    2001-12-01

    Along with the development of living standard, people's demand for food quality and food hygiene also rises. People demand food not only with rich nutrition, inexpensive price, but also with safety. So food hygiene test is paid common attention of society. Milk is a nourishing food and is loved by people. Sour milk goods from milk is also in great demand. But nourishing foods are good for growing many microbes. Fresh milk and sour milk are easy contaminated by microbes and go bad. Laser-induced fluorescence (LIF) technology is an important part of modern optics. It is broadly applied in biomedicine, diagnostics, test of food hygiene, environment protecting, owing to its high sensitivity, high speed, automation, untouched testing. In this paper, we attempted to LIF technology to test milk food quality. We used the third harmonics pulsed Nd:YAG laser (355 nm) as the exciting source, and a multi-track spectrometer as the detector and measured the intensities of apply LIF of fresh milk and sour milk during their deteriorating course. Test system and test method are introduced, fluorescence spectra of deteriorating course are also attached. The test result makes clear that there are close connection between deteriorating course and fluorescence spectra.

  8. Effects of isoflurane on measurement of fluorescence spectra and CLSM imaging in Acetabularia acetabulum

    NASA Astrophysics Data System (ADS)

    Chen, WenLi; Quan, Zhou; Xing, Da

    2007-05-01

    The volatile halogenated methyl ethyl ether is used as anesthetic to inhibit actin-based dynamics directly or indirectly in animal cells. In plant cells, most intracellular movements are related with actin pathways too. We utilized isoflurane to study the dynamic choloroplast organization in unicellular baby and adult alga Acetabularia acetabulum. Fluorescence spectra were measured and choloroplast movements were recorded by confocal laser scanning microscope (CLSM) imaging in in Acetabularia acetabulum. Isoflurane was effective in the unicellular baby and adult organisms and showed time- dependent actin-inhibition patterns. Acetabularia acetabulum cells were treated for different times with isoflurane saturated solutions in artificial seawater (it was defined to be 100% isoflurane). The intensity of fluorescence at 680nm and 730nm were progressively decreased at 100% isoflurane. It was remarkable difference between fluorescence spectra of baby and adult Acetabularia were inhibited by isoflurance, adult Acetabularia cells showed more sensitive. Whereas the choloroplast in Acetabularia acetabulum was commendably imaged by CLSM at 20 and 40 zoom.

  9. Evaluation of algorithm methods for fluorescence spectra of cancerous and normal human tissues

    NASA Astrophysics Data System (ADS)

    Pu, Yang; Wang, Wubao; Alfano, Robert R.

    2016-03-01

    The paper focus on the various algorithms on to unravel the fluorescence spectra by unmixing methods to identify cancerous and normal human tissues from the measured fluorescence spectroscopy. The biochemical or morphologic changes that cause fluorescence spectra variations would appear earlier than the histological approach; therefore, fluorescence spectroscopy holds a great promise as clinical tool for diagnosing early stage of carcinomas and other deceases for in vivo use. The method can further identify tissue biomarkers by decomposing the spectral contributions of different fluorescent molecules of interest. In this work, we investigate the performance of blind source un-mixing methods (backward model) and spectral fitting approaches (forward model) in decomposing the contributions of key fluorescent molecules from the tissue mixture background when certain selected excitation wavelength is applied. Pairs of adenocarcinoma as well as normal tissues confirmed by pathologist were excited by selective wavelength of 340 nm. The emission spectra of resected fresh tissue were used to evaluate the relative changes of collagen, reduced nicotinamide adenine dinucleotide (NADH), and Flavin by various spectral un-mixing methods. Two categories of algorithms: forward methods and Blind Source Separation [such as Principal Component Analysis (PCA) and Independent Component Analysis (ICA), and Nonnegative Matrix Factorization (NMF)] will be introduced and evaluated. The purpose of the spectral analysis is to discard the redundant information which conceals the difference between these two types of tissues, but keep their diagnostically significance. The facts predicted by different methods were compared to the gold standard of histopathology. The results indicate that these key fluorophores within tissue, e.g. tryptophan, collagen, and NADH, and flavin, show differences of relative contents of fluorophores among different types of human cancer and normal tissues. The

  10. Aprotic solvents effect on the UV-visible absorption spectra of bixin

    NASA Astrophysics Data System (ADS)

    Rahmalia, Winda; Fabre, Jean-François; Usman, Thamrin; Mouloungui, Zéphirin

    2014-10-01

    We describe here the effects of aprotic solvents on the spectroscopic characteristics of bixin. Bixin was dissolved in dimethyl sulfoxide, acetone, dichloromethane, ethyl acetate, chloroform, dimethyl carbonate, cyclohexane and hexane, separately, and its spectra in the resulting solutions were determined by UV-visible spectrophotometry at normal pressure and room temperature. We analyzed the effect of aprotic solvents on λmax according to Onsager cavity model and Hansen theory, and determined the approximate absorption coefficient with the Beer-Lambert law. We found that the UV-visible absorption spectra of bixin were found to be solvent dependent. The S0 → S2 transition energy of bixin in solution was dependent principally on the refractive index of the solvents and the bixin-solvent dispersion interaction. There was a small influence of the solvents dielectric constant, permanent dipole interaction and hydrogen bonding occurred between bixin and solvents. The absorbance of bixin in various solvents, with the exception of hexane, increased linearly with concentration.

  11. Aprotic solvents effect on the UV-visible absorption spectra of bixin.

    PubMed

    Rahmalia, Winda; Fabre, Jean-François; Usman, Thamrin; Mouloungui, Zéphirin

    2014-10-15

    We describe here the effects of aprotic solvents on the spectroscopic characteristics of bixin. Bixin was dissolved in dimethyl sulfoxide, acetone, dichloromethane, ethyl acetate, chloroform, dimethyl carbonate, cyclohexane and hexane, separately, and its spectra in the resulting solutions were determined by UV-visible spectrophotometry at normal pressure and room temperature. We analyzed the effect of aprotic solvents on λmax according to Onsager cavity model and Hansen theory, and determined the approximate absorption coefficient with the Beer-Lambert law. We found that the UV-visible absorption spectra of bixin were found to be solvent dependent. The S0→S2 transition energy of bixin in solution was dependent principally on the refractive index of the solvents and the bixin-solvent dispersion interaction. There was a small influence of the solvents dielectric constant, permanent dipole interaction and hydrogen bonding occurred between bixin and solvents. The absorbance of bixin in various solvents, with the exception of hexane, increased linearly with concentration. PMID:24840486

  12. Plasmonic resonance absorption spectra in mid-infrared in an array of graphene nanoresonators

    NASA Astrophysics Data System (ADS)

    Abeysinghe, Don C.; Myers, Joshua; Nader Esfahani, Nima; Hendrickson, Joshua R.; Cleary, Justin W.; Walker, Dennis E.; Chen, Kuei-Hsien; Chen, Li-Chyong; Mou, Shin

    2013-12-01

    We experimentally demonstrated graphene plasmon resonant absorption in mid-IR by utilizing an array of graphene nanoribbon resonators on SiO2 substrate. By tuning resonator width we probed the graphene plasmons with λp <= λ0/100 and plasmon resonances as high as 0.240 eV (2100 cm-1) for 40 nm wide nanoresonators. Resonant absorption spectra revealed plasmon dispersion as well as plasmon damping due to the interaction of graphene plasmons with the surface polar phonons in SiO2 substrate and intrinsic graphene optical phonons. Graphene nanoribbons with varying widths enabled us to identify the damping mechanisms of graphene plasmons and much reduced damping was observed when the plasmon resonance frequencies were close to the substrate polar phonon frequencies. Then, by direct ebeam exposure of graphene nanoresonators, we effectively changed the carrier density and caused red-shift of the plasmon spectra. This work will provide insight into light-sensitive, frequency-tunable photodetectors based on graphene's plasmonic excitations.

  13. Removal of Mars atmospheric gas absorption from Phobos-2/ISM spectra

    NASA Astrophysics Data System (ADS)

    Castronuovo, M. M.; Ulivieri, C.

    Infrared imaging spectrometer (ISM) is an imaging spectrometer in the range of the near infrared that flew onboard of Soviet probe Phobos 2 in 1989. Its first objective was to obtain information about the mineralogic composition of the soil of Mars and its satellite Phobos, and about the spatial and temporal variability of the Martian atmosphere. In the spectral range of the instrument 0.76-3.16 microns, the radiation emerging from Mars' atmosphere is almost entirely due to the solar radiation reflected by the soil. Therefore, independent knowledge of the spectral transmittance of the atmosphere allows us to eliminate the atmospheric effect from the ISM data and so to obtain the spectral signature of the planet soil. In the present work the Martian atmospheric transmittance has been computed using FASCODE and the spectral lines atlas HITRAN of AFGL. The atmospheric profile has been defined on the basis of the work of Moroz et al. Then, the convolution of the computed transmittance with the response functions of ISM has been carried out to obtain the atmospheric absorption from the measurements it is necessary to renormalize the transmittance computed with FASCODE so that the depth of the absorption bands is the same as that of the bands measured by ISM. Finally, dividing the measured spectra by the computed ones we obtain the spectra signature of Martian soil from which it is possible to deduce the mineralogical composition of the observed zones.

  14. Absorption spectra of e-beam-excited Ne, Ar, and Kr, pure and in binary mixtures.

    PubMed

    Levchenko, A O; Ustinovskii, N N; Zvorykin, V D

    2010-10-21

    A technique using the broadband emission of a laser plume as probe radiation is applied to record UV-visible (190-510 nm) absorption spectra of Ne, Ar, and Kr, pure and in binary mixtures under moderate e-beam excitation up to 1 MW/cm(3). In all the rare gases and mixtures, the absorption spectra show continuum related to Rg(2) (+) homonuclear ions [peaking at λ∼285, 295, and 320 nm in Ne, Ar, and Kr(Ar/Kr), respectively] and a number of atomic lines related mainly to Rg(∗)(ms) levels, where m is the lowest principal quantum number of the valence electron. In argon, a continuum related to Ar(2) (∗) (λ∼325 nm) is also recorded. There are also trains of narrow bands corresponding to Rg(2) (∗)(npπ (3)Π(g))←Rg(2) (∗)(msσ (3)Σ(u) (+)) transitions. All the spectral features mentioned above were reported in literature but have never been observed simultaneously. Although charge transfer to a homonuclear ion of the heavier additive is commonly believed to dominate in binary rare-gas mixtures, it is found in this study that in Ne/Kr mixture, the charge is finally transferred from the buffer gas Ne(2) (+) ion not to Kr(2) (+) but to heteronuclear NeKr(+) ion.

  15. Anisotropy of optical absorption spectra of rare-earth orthoaluminate DyAlO3

    NASA Astrophysics Data System (ADS)

    Valiev, U. V.; Gruber, J. B.; Rakhimov, Sh. A.; Nabelkin, O. A.

    2003-06-01

    The polarization spectra of optical absorption for the 4f-4f transition 6H15/2 6F3/2 and 6H15/2 6F5/2 in the rare-earth orthoaluminate DyAlO3 have been studied experimentally at the temperature T = 78 K. It has been shown that the non-trivial character of the polarization absorption spectra anisotropy for low temperatures can be explained by a contribution of the J-J mixing mechanism for the excited multiplets of the ground 4f(n) configuration of the Dy3+ ion in the low-symmetry crystalline field in the orthoaluminate structure. The results of numerical calculations of energies and wave functions of the Stark sublevels of the excited multiplets 6F3/2 and 6F5/2 are presented for the ground 4f9 configuration of the rare-earth Dy3+ ion in the crystalline field of Cs symmetry.

  16. A wavelet analysis for the X-ray absorption spectra of molecules

    SciTech Connect

    Penfold, T. J.; Tavernelli, I.; Rothlisberger, U.; Milne, C. J.; Abela, R.; Reinhard, M.; Nahhas, A. El; Chergui, M.

    2013-01-07

    We present a Wavelet transform analysis for the X-ray absorption spectra of molecules. In contrast to the traditionally used Fourier transform approach, this analysis yields a 2D correlation plot in both R- and k-space. As a consequence, it is possible to distinguish between different scattering pathways at the same distance from the absorbing atom and between the contributions of single and multiple scattering events, making an unambiguous assignment of the fine structure oscillations for complex systems possible. We apply this to two previously studied transition metal complexes, namely iron hexacyanide in both its ferric and ferrous form, and a rhenium diimine complex, [ReX(CO){sub 3}(bpy)], where X = Br, Cl, or ethyl pyridine (Etpy). Our results demonstrate the potential advantages of using this approach and they highlight the importance of multiple scattering, and specifically the focusing phenomenon to the extended X-ray absorption fine structure (EXAFS) spectra of these complexes. We also shed light on the low sensitivity of the EXAFS spectrum to the Re-X scattering pathway.

  17. Two-Photon Absorption Laser Induced Fluorescence Measurements of Neutral Density in Helicon Plasma

    NASA Astrophysics Data System (ADS)

    Galante, Matthew

    2013-10-01

    Neutral particles play a critical role in nearly all plasmas, from the pedestal region of a tokamak fusion plasma to industrial plasma processing systems. In fusion plasmas, neutrals at the edge serve as both a source of particles and also a sink of momentum and energy. Control of the edge plasma density in tokamaks is critical for the transition to H-mode plasmas and the role of neutrals in modifying the plasma rotation in the edge is an area of active research. However, few methods exist to make localized, direct neutral density measurements. We have developed a new diagnostic based on two-photon absorption laser induced fluorescence (TALIF). We use a high intensity (5 MW/cm2), narrow bandwidth (0.1 cm-1) laser to probe the ground state of neutral hydrogen, deuterium and krypton with spatial resolution better than 0.2 cm, a time resolution of 10 ns, and a measurement cadence of 20 Hz. In this talk I will describe proof-of-principle measurements in a helicon plasma source that demonstrate the TALIF diagnostic is capable of measuring neutral densities spanning four orders of magnitude; comparable to the edge neutral gradients predicted in the tokamak pedestal. The measurements are performed in hydrogen and deuterium plasmas and absolute calibration is accomplished through TALIF measurements in neutral krypton. The optical configuration employed is confocal, i.e., both light injection and collection are accomplished through a single optical port in the vacuum vessel. The wavelength resolution of the diagnostic is sufficient to separate hydrogen and deuterium spectra and I will present measurements from mixed hydrogen and deuterium plasmas that demonstrate isotopic abundance measurements are feasible with the TALIF system. Time and spatially resolved measurements also allow us to explore the effects of wall recycling and pulse repetition rates on the neutral density profile in the plasma source. Work supported in part by US DOE under DE-FC02-04ER54698.

  18. Two photon absorption laser induced fluorescence measurements of neutral density in a helicon plasmaa)

    NASA Astrophysics Data System (ADS)

    Galante, M. E.; Magee, R. M.; Scime, E. E.

    2014-05-01

    We have developed a new diagnostic based on two-photon absorption laser induced fluorescence (TALIF). We use a high intensity (5 MW/cm2), narrow bandwidth (0.1 cm-1) laser to probe the ground state of neutral hydrogen, deuterium and krypton with spatial resolution better than 0.2 cm, a time resolution of 10 ns, and a measurement cadence of 20 Hz. Here, we describe proof-of-principle measurements in a helicon plasma source that demonstrate the TALIF diagnostic is capable of measuring neutral densities spanning four orders of magnitude; comparable to the edge neutral gradients predicted in the DIII-D tokamak pedestal. The measurements are performed in hydrogen and deuterium plasmas and absolute calibration is accomplished through TALIF measurements in neutral krypton. The optical configuration employed is confocal, i.e., both light injection and collection are accomplished with a single lens through a single optical port in the vacuum vessel. The wavelength resolution of the diagnostic is sufficient to separate hydrogen and deuterium spectra and we present measurements from mixed hydrogen and deuterium plasmas that demonstrate isotopic abundance measurements are feasible. Time resolved measurements also allow us to explore the evolution of the neutral hydrogen density and temperature and effects of wall recycling. We find that the atomic neutral density grows rapidly at the initiation of the discharge, reaching the steady-state value within 1 ms. Additionally, we find that neutral hydrogen atoms are born with 0.08 eV temperatures, not 2 eV as is typically assumed.

  19. Two photon absorption laser induced fluorescence measurements of neutral density in a helicon plasma

    SciTech Connect

    Galante, M. E.; Magee, R. M.; Scime, E. E.

    2014-05-15

    We have developed a new diagnostic based on two-photon absorption laser induced fluorescence (TALIF). We use a high intensity (5 MW/cm{sup 2}), narrow bandwidth (0.1 cm{sup −1}) laser to probe the ground state of neutral hydrogen, deuterium and krypton with spatial resolution better than 0.2 cm, a time resolution of 10 ns, and a measurement cadence of 20 Hz. Here, we describe proof-of-principle measurements in a helicon plasma source that demonstrate the TALIF diagnostic is capable of measuring neutral densities spanning four orders of magnitude; comparable to the edge neutral gradients predicted in the DIII-D tokamak pedestal. The measurements are performed in hydrogen and deuterium plasmas and absolute calibration is accomplished through TALIF measurements in neutral krypton. The optical configuration employed is confocal, i.e., both light injection and collection are accomplished with a single lens through a single optical port in the vacuum vessel. The wavelength resolution of the diagnostic is sufficient to separate hydrogen and deuterium spectra and we present measurements from mixed hydrogen and deuterium plasmas that demonstrate isotopic abundance measurements are feasible. Time resolved measurements also allow us to explore the evolution of the neutral hydrogen density and temperature and effects of wall recycling. We find that the atomic neutral density grows rapidly at the initiation of the discharge, reaching the steady-state value within 1 ms. Additionally, we find that neutral hydrogen atoms are born with 0.08 eV temperatures, not 2 eV as is typically assumed.

  20. Re-Analysis of the Dispersed Fluorescence Spectra of the C_3-RARE Gas Atom Complexes

    NASA Astrophysics Data System (ADS)

    Wang, Yi-Jen; Merer, Anthony; Hsu, Yen-Chu

    2015-06-01

    The dispersed fluorescence (DF) spectra of the C_3Ne, C_3Ar, C_3Kr, and C_3Xe complexes near the 0 2^- 0- 000, 0 4^- 0- 000, 0 2^+ 0- 000 and 100-000 bands of the {A}- {X} system of C_3 have been revisited. Some of the DF spectra of the Ne and Ar complexes have been recently obtained with a slightly improved resolution of 6-10 wn. All the DF spectra have been reassigned as emission from van der Waals (vdW) complexes and C_3 fragments. The optically excited C_3-Rg (Rg = rare-gas atom) complexes fluorescence and/or decay down to slightly lower (about 2-30 wn) vibrational levels without changing the internal energy of C_3 and then predissociate via the continua of the nearby vibronic states of C_3. The available dissociation channels depend on the binding energy of the ground electronic state complex. Exceptions have been found at the vdW bands near the 0 4^- 0- 000 band of C_3. The binding energies of the ground electronic states of these four complexes will be discussed. G. Zhang, B.-G. Lin, S.-M. Wen, and Y.-C. Hsu, J. Chem. Phys. 20, 3189(2004) J.-M. Chao, K. S. Tham, G. Zhang, A. J. Merer, Y.-C. Hsu, and W.-P. Hu, J. Chem. Phys. 34, 074313(2011)

  1. Probability-based differential normalized fluorescence bivariate analysis for the classification of tissue autofluorescence spectra.

    PubMed

    Wang, Gufeng; Platz, Charles P; Geng, M Lei

    2006-05-01

    Differential normalized fluorescence (DNF) is an efficient and effective method for the differentiation of normal and cancerous tissue fluorescence spectra. The diagnostic features are extracted from the difference between the averaged cancerous and averaged normal tissue spectra and used as indices in tissue classification. In this paper, a new method, probability-based DNF bivariate analysis, is introduced based on the univariate DNF method. Two differentiation features are used concurrently in the new method to achieve better classification accuracy. The probability of each sample belonging to a disease state is determined with Bayes decision theory. This probability approach classifies the tissue spectra according to disease states and provides uncertainty information on classification. With a data set of 57 colonic tissue sites, probability-based DNF bivariate analysis is demonstrated to improve the accuracy of cancer diagnosis. The bivariate DNF analysis only requires the collection of a few data points across the entire emission spectrum and has the potential of improving data acquisition speed in tissue imaging.

  2. Simulating One-Photon Absorption and Resonance Raman Scattering Spectra Using Analytical Excited State Energy Gradients within Time-Dependent Density Functional Theory

    SciTech Connect

    Silverstein, Daniel W.; Govind, Niranjan; van Dam, Hubertus J. J.; Jensen, Lasse

    2013-12-10

    A parallel implementation of analytical time-dependent density functional theory gradients is presented for the quantum chemistry program NWChem. The implementation is based on the Lagrangian approach developed by Furche and Ahlrichs. To validate our implementation, we first calculate the Stokes shifts for a range of organic dye molecules using a diverse set of exchange-correlation functionals (traditional density functionals, global hybrids, and range-separated hybrids) followed by simulations of the one-photon absorption and resonance Raman scattering spectrum of the phenoxyl radical, the well-studied dye molecule rhodamine 6G, and a molecular host–guest complex (TTFcCBPQT4+). The study of organic dye molecules illustrates that B3LYP and CAM-B3LYP generally give the best agreement with experimentally determined Stokes shifts unless the excited state is a charge transfer state. Absorption, resonance Raman, and fluorescence simulations for the phenoxyl radical indicate that explicit solvation may be required for accurate characterization. For the host–guest complex and rhodamine 6G, it is demonstrated that absorption spectra can be simulated in good agreement with experimental data for most exchange-correlation functionals. Finally, however, because one-photon absorption spectra generally lack well-resolved vibrational features, resonance Raman simulations are necessary to evaluate the accuracy of the exchange-correlation functional for describing a potential energy surface.

  3. The nonlinear spectra of transneptunian objects: Evidence for organic absorption bands

    NASA Astrophysics Data System (ADS)

    Fraser, W.; Brown, M.; Emery, J.

    2014-07-01

    The reflectance spectra of small (D≲250 km) transneptunian objects (TNOs) are generally quite simple. Water-ice absorption is the only feature firmly detected on the majority of TNOs (Brown et al. 2012). Tentative detections of other materials have been presented (e.g., Barucci et al. 2011), but generally speaking, the spectra of small TNOs are nearly linear in the optical (0.5 < λ < 0.9 μ m; Fornasier et al. 2009) and NIR ranges (1.0 < λ < 1.5 μ m) with water-ice absorption apparent at longer wavelengths (Barkume et al. 2008). Each region is well described by a spectral slope, with the optical slope being typically redder than in the NIR (Hainaut and Delsanti, 2002, 2012). Here we present new spectral photometry of two TNOs which do not fit this simple prescription. We will present photometry of TNOs taken from HST during cycles 17 and 18. Unlike most objects, two TNOs do not exhibit linear optical spectra. Rather, they exhibit upward curvatures shortward of λ ˜ 1 μ m, with colors becoming redder with increasing wavelength. Previously published spectra and photometry exhibit similar optical shapes on a number of TNOs, including Borasisi, Pholus, Chariklo, Asbolus, and 2003 AZ_{84} (Romon-Martin et al. 2002, Alvarez-Candal et al. 2008, Fornasier 2009, Hainaut and Delsanti 2012). An interesting candidate for the upward curvature is complex C- and N-bearing hydrocarbons. These organic materials exhibit a broad absorption centered in the UV which is caused by a valence-conduction energy gap (see Moroz et al. 1998). The specific shape of the feature depends on the molecular structure of the organic material, with longer hydrocarbons generally producing wider absorptions. The assertion that the optical spectra of small TNOs are influenced by this hydrocarbon feature is reasonable as the feature is the general result of irradiation of simple organic H-, C-, and N-bearing materials, not dissimilar to that expected to occur on young TNOs (Brunetto et al. 2006

  4. Metal-free phthalocyanine aggregation and binding with amines: Specific and general solvent effects on absorption and fluorescence properties

    NASA Astrophysics Data System (ADS)

    Wang, Tao; Zhang, Xian-Fu; Lu, Xulin

    2015-03-01

    The fluorescence and absorption properties of a metal-free phthalocyanine (Pc) H2PcR4 and its zinc-centered complex ZnPcR4 (R is the isopropyloxy at the β-position of a Pc ring) were measured and compared in protic and aprotic solvents. H2PcR4 shows strong bonding interaction with amines and aggregation in alcohols in addition to the general solvent effect in aprotic solvents due to polarity change. The specific solvent effect leads to substantial changes in its spectra, fluorescence quantum yield (Φf) and fluorescence lifetime (τf) values. In contrast, ZnPcR4 does not show the specific effects due to the presence of a central element in a Pc cavity. For H2PcR4 the change of solvents caused a large variation of Φf (0.050-0.48) and τf (3.45-6.88 ns), in contrast to the slight changes for ZnPcR4. On the other hand, the general solvent effect of H2PcR4 due to polarity is also more significant than that of ZnPcR4. The increase of solvent polarity decreases both Φf and τf, but increases the Stoke's shift.

  5. [Absorption and fluorescence characteristics of dissolved organic matter (DOM) in rainwater and sources analysis in summer and winter season].

    PubMed

    Liang, Jian; Jiang, Tao; WeiI, Shi-Qiang; Lu, Song; Yan, Jin-Long; Wang, Qi-Lei; Gao, Jie

    2015-03-01

    This study aimed at evaluating the variability of the optical properties including UV-Vis and fluorescence characteristics of dissolved organic matter (DOM) from rainwater in summer and winter seasons. UV-Vis and fluorescence spectroscopy, together with Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model and fire events map, were conducted to characterize DOM and investigate its sources and contributions. The results showed that as compared with aquatic and soil DOM, rainwater DOM showed similar spectral characteristics, suggesting DOM in precipitation was also an important contributor to DOM pool in terrestrial and aquatic systems. The concentrations of DOC in rainwater were 0.88-12.80 mg x L(-1), and the CDOM concentrations were 3.17-21.11 mg x L(-1). Differences of DOM samples between summer and winter were significant (P < 0.05). In comparison to summer, DOM samples in winter had lower molecular weight and aromaticity, and also lower humification. Input of DOM in winter was predominantly derived from local and short-distance distances, while non-special scattering sources were identified as the main contributors in summer. Although absorption and fluorescence spectroscopy could be used to identify DOM composition and sources, there were obvious differences in spectra and sources analysis between rainwater DOM and the others from other sources. Thus, the classic differentiation method by "allochthonous (terrigenous) and autochthonous (authigenic)" is possibly too simple and arbitrary for characterization of DOM in rainwater.

  6. Infrared absorption spectra of a Nd0.5Ho0.5Fe3(BO3)4 crystal

    NASA Astrophysics Data System (ADS)

    Gerasimova, Yu. V.; Sofronova, S. N.; Gudim, I. A.; Oreshonkov, A. S.; Vtyurin, A. N.; Ivanenko, A. A.

    2016-01-01

    Infrared absorption spectra of a Nd0.5Ho0.5Fe3(BO3)4 crystal in the spectral range of 30-1700 cm-1 have been measured at temperatures from 6 to 300 K. The experimental spectra have been analyzed based on the semiempirical calculation of the lattice dynamics and the analysis of correlation diagrams of borate complexes. No changes associated with structural phase transitions have been detected in the temperature range of measurements; the effect of magnetic ordering on the infrared absorption spectra has not been observed.

  7. Ultrafast absorption difference spectra of the Fenna-Matthews-Olson protein at 19 K: experiment and simulations.

    PubMed

    Buck, D R; Savikhin, S; Struve, W S

    1997-01-01

    We describe simulations of absorption difference spectra in strongly coupled photosynthetic antennas. In the presence of large resonance couplings, distinctive features arise from excited-state absorption transitions between one- and two-exciton levels. We first outline the theory for the heterodimer and for the general N-pigment system, and we demonstrate the transition between the strong and weak coupling regimes. The theory is applied to Fenna-Matthews-Olson (FMO) bacteriochlorophyll a protein trimers from the green photosynthetic bacterium Prosthecochloris aestuarii and then compared with experimental low-temperature absorption difference spectra of FMO trimers from the green bacterium Chlorobium tepidum.

  8. Exciton-Like Behavior in Low-Energy Absorption Spectra of Simple Alloys

    NASA Astrophysics Data System (ADS)

    Bakshi, Mira Hemendraray

    The valence excitation (ns('2) (--->) nsnp) spectra of Mg, Zn, and Ca impurities at various concentrations in Li have been measured. Polarization modulation ellipsometry was used to determine the impurity-induced changes in real and imaginary parts of the dielectric function simultaneously, together with the differential reflectivity, in the energy range 1.5 - 4.5 eV. The most important result at sufficiently dilute alloy compositions, is that the system investigated display a distinct absorption peak above the Drude background. The height of this peak varies linearly with impurity content. The impurity-specific character of these spectral features points to exciton-like behavior at low-energy, arising from atomic-like excitations in which the electron and the hole linger together at the impurity site. Existing theories of alloy spectra do not explain these effects, because they do not include the Coulomb correlations between the interacting quasiparticles created in the optical event, or the way in which the interacting pair is confined to the impurity site by the mutual field. A remarkable added result of this research is that the exciton-like behavior can be followed with increasing impurity content, all the way to the pure Mg response, when it becomes the interband transition. This has led Kunz and Flynn to reformulate the theory of optical absorption including excited state interactions; and to apply the theory to the spectrum of pure Mg. The Coulomb interaction causes striking effects which are in generally good agreement with experiment. Zn-Li alloys behave differently. At an alloy composition for which Zn-Zn interactions become prevalent, the local, impurity-specific character of the spectrum disappears, leaving only a featureless Drude-like absorption. These results have provoked cluster calculations by Boisvert and Kunz, which predict the spectral shifts, and exhibit qualitatively similar persistence for Mg-Li, and broadening for Zn-Li.

  9. Stratospheric N2O mixing ratio profile from high-resolution balloon-borne solar absorption spectra and laboratory spectra near 1880/cm

    NASA Technical Reports Server (NTRS)

    Rinsland, C. P.; Goldman, A.; Murcray, F. J.; Murcray, D. G.; Smith, M. A. H.; Seals, R. K., Jr.; Larsen, J. C.; Rinsland, P. L.

    1982-01-01

    A nonlinear least-squares fitting procedure is used to derive the stratospheric N2O mixing ratio profile from balloon-borne solar absorption spectra and laboratory spectra near 1880/cm. The atmospheric spectra analyzed here were recorded during sunset from a float altitude of 33 km with the University of Denver's 0.02/cm resolution interferometer near Alamogordo, N.M. (33 deg N) on Oct. 10, 1979. The laboratory data are used to determine the N2O line intensities. The measurements suggest an N2O mixing ratio of 264 ppbv near 15 km, decreasing to 155 ppbv near 28 km.

  10. Stratospheric N(2)O mixing ratio profile from high-resolution balloon-borne solar absorption spectra and laboratory spectra near 1880 cm(-1).

    PubMed

    Rinsland, C P; Goldman, A; Murcray, F J; Murcray, D G; Smith, M A; Seals, R K; Larsen, J C; Rinsland, P L

    1982-12-01

    A nonlinear least-squares fitting procedure has been used to derive the stratospheric N(2)O mixing ratio profile from balloon-borne solar absorption spectra and laboratory spectra near 1880 cm(-1). The atmospheric spectra were recorded during sunset from a float altitude of 33 km with the University of Denver 0.02-cm(-1) resolution interferometer near Alamogordo, N.M. (33 degrees N), on 10 Oct. 1979. The laboratory data were used to determine the N(2)O line intensities. The measurements indicate an N(2)O mixing ratio of 264 ppbv near 15 km decreasing to 155 ppbv near 28 km. PMID:20401069

  11. Stratospheric N2O mixing ratio profile from high-resolution balloon-borne solar absorption spectra and laboratory spectra near 1880/cm

    NASA Astrophysics Data System (ADS)

    Rinsland, C. P.; Goldman, A.; Murcray, F. J.; Murcray, D. G.; Smith, M. A. H.; Seals, R. K., Jr.; Larsen, J. C.; Rinsland, P. L.

    1982-12-01

    A nonlinear least-squares fitting procedure is used to derive the stratospheric N2O mixing ratio profile from balloon-borne solar absorption spectra and laboratory spectra near 1880/cm. The atmospheric spectra analyzed here were recorded during sunset from a float altitude of 33 km with the University of Denver's 0.02/cm resolution interferometer near Alamogordo, N.M. (33 deg N) on Oct. 10, 1979. The laboratory data are used to determine the N2O line intensities. The measurements suggest an N2O mixing ratio of 264 ppbv near 15 km, decreasing to 155 ppbv near 28 km.

  12. Phase speed spectra of transient eddy fluxes and critical layer absorption

    NASA Technical Reports Server (NTRS)

    Randel, William J.; Held, Isaac M.

    1991-01-01

    Tropospheric zonal mean eddy fluxes of heat and momentum, and the divergence of the Eliassen-Palm flux, are decomposed into contributions from different zonal phase speeds. Data analyzed are the European Center for Medium Range Weather Forecasts operational global analyses covering 1980-1987. Eastward moving medium-scale waves (zonal waves 4-7) dominate the spectra of lower tropospheric heat fluxes in both hemispheres and all seasons. Upper tropospheric wave flux spectra are similar to the low level spectra in midlatitudes, but shift to slower zonal phase speeds as low latitudes are approached. The cause of this shift is the selective absorption of faster moving components in midlatitudes as the waves propagate meridionally. Latitude-phase speed distributions of eddy fluxes are constructed and compared to the zonal mean wind structure. These results demonstrate that upper tropospheric eddies break and decelerate the zonal mean flow approximately 10-20 deg in latitude away from their critical line (where phase speed equals zonal wind speed). Comparisons are also made with results from the middle stratosphere.

  13. Plastocyanin conformation: an analysis of its near ultraviolet absorption and circular dichroic spectra

    SciTech Connect

    Draheim, J.E.; Anderson, G.P.; Duane, J.W.; Gross, E.L.

    1986-04-01

    The near-ultraviolet absorption and circular dichroic spectra of plastocyanin are dependent upon the redox state, solution pH, and ammonium sulfate concentration. This dependency was observed in plastocyanin isolated from spinach, poplar, and lettuce. Removal of the copper atom also perturbed the near-ultraviolet spectra. Upon reduction there are increases in both extinction and ellipticity at 252 nm. Further increases at 252 nm were observed upon formation of apo plastocyanin eliminating charge transfer transitions as the cause. The spectral changes in the near-ultraviolet imply a flexible tertiary conformation for plastocyanin. There are at least two charge transfer transitions at approx.295-340 nm. One of these transitions is sensitive to low pH's and is attributed to the His 87 copper ligand. The redox state dependent changes observed in the near-ultraviolet spectra of plastocyanin are attenuated either by decreasing the pH to 5 or by increasing the ammonium sulfate concentration to 2.7 M. This attenuation cannot be easily explained by simple charge screening. Hydrophobic interactions probably play an important role in this phenomenon. The pH and redox state dependent conformational changes may play an important role in regulating electron transport.

  14. Quantitative comparisons of absorption cross-section spectra and integrated intensities of HFC-143a

    NASA Astrophysics Data System (ADS)

    Le Bris, Karine; Graham, Laura

    2015-01-01

    The integrated absorption cross-sections of HFC-143a (CH3CF3) differ substantially in the literature. This leads to an important uncertainty on the value of the radiative efficiency of this molecule. The ambiguity on the absorption cross-sections of HFC-143a is highlighted by the existence of two significantly different datasets in the HITRAN database. To solve the issue, we performed high-resolution Fourier transform infrared laboratory measurements of HFC-13a and compared the spectra with the two HITRAN datasets and with the data from the Pacific Northwest National Laboratory (PNNL). The experimental methods and data analysis techniques are examined and typical sources of errors are discussed. The integrated intensities of the main bands are compared to other literature values. It was found that the integrated absorption cross-section values in the highest range - around 13.8 ×10-17 cm .molecule-1 in the 570-1500 cm-1 spectral band - show the most consistency between authors.

  15. Absorption-Mode Fourier Transform Mass Spectrometry: The Effects of Apodization and Phasing on Modified Protein Spectra

    NASA Astrophysics Data System (ADS)

    Qi, Yulin; Li, Huilin; Wills, Rebecca H.; Perez-Hurtado, Pilar; Yu, Xiang; Kilgour, David P. A.; Barrow, Mark P.; Lin, Cheng; O'Connor, Peter B.

    2013-06-01

    The method of phasing broadband Fourier transform ion cyclotron resonance (FT-ICR) spectra allows plotting the spectra in the absorption-mode; this new approach significantly improves the quality of the data at no extra cost. Herein, an internal calibration method for calculating the phase function has been developed and successfully applied to the top-down spectra of modified proteins, where the peak intensities vary by 100×. The result shows that the use of absorption-mode spectra allows more peaks to be discerned within the recorded data, and this can reveal much greater information about the protein and modifications under investigation. In addition, noise and harmonic peaks can be assigned immediately in the absorption-mode.

  16. Laboratory studies at high resolution of the infrared absorption spectra of a number of gases found in planetary atmospheres

    NASA Technical Reports Server (NTRS)

    Hunt, R. H.

    1983-01-01

    The infrared absorption spectra of a number of gases found in planetary atmospheres were studied at high resolution. Absorption line measurements which can be of value for the interpretation of planetary spectra in terms of molecular abundances and conditions in the planetary atmospheres were provided. The high resolution spectra have yielded measurements of individual vibration rotation line parameters including positions, strengths, pressure broadened widths and, where assignments were unknown, the temperature sensitivity of the strengths. Such information allows the determinations of the absorption of a given molecular gas under planetary conditions of temperature and pressure and at the same time it provides the data necessary if the spectra are to be understood in terms of basic molecular theory. Thus this work has included spectral analysis in the form of line assignments as well as fitting of the data to Hamiltonian models. Such fitting is very useful in that it helps to confirm and extend the assignments.

  17. Absorption-mode Fourier transform mass spectrometry: the effects of apodization and phasing on modified protein spectra.

    PubMed

    Qi, Yulin; Li, Huilin; Wills, Rebecca H; Perez-Hurtado, Pilar; Yu, Xiang; Kilgour, David P A; Barrow, Mark P; Lin, Cheng; O'Connor, Peter B

    2013-06-01

    The method of phasing broadband Fourier transform ion cyclotron resonance (FT-ICR) spectra allows plotting the spectra in the absorption-mode; this new approach significantly improves the quality of the data at no extra cost. Herein, an internal calibration method for calculating the phase function has been developed and successfully applied to the top-down spectra of modified proteins, where the peak intensities vary by 100×. The result shows that the use of absorption-mode spectra allows more peaks to be discerned within the recorded data, and this can reveal much greater information about the protein and modifications under investigation. In addition, noise and harmonic peaks can be assigned immediately in the absorption-mode.

  18. Calculation of vibrational and electronic excited state absorption spectra of arsenic-water complexes using density functional theory

    NASA Astrophysics Data System (ADS)

    Huang, L.; Lambrakos, S. G.; Shabaev, A.; Massa, L.

    2016-05-01

    Calculations are presented of vibrational and electronic excited-state absorption spectra for As-H2O complexes using density function theory (DFT) and time-dependent density functional theory (TD-DFT). DFT and TD-DFT can provide interpretation of absorption spectra with respect to molecular structure for excitation by electromagnetic waves at frequencies within the IR and UV-visible ranges. The absorption spectrum corresponding to excitation states of As-H2O complexes consisting of relatively small numbers of water molecules should be associated with response features that are intermediate between that of isolated molecules and that of a bulk system. DFT and TD-DFT calculated absorption spectra represent quantitative estimates that can be correlated with additional information obtained from laboratory measurements and other types of theory based calculations. The DFT software GAUSSIAN was used for the calculations of excitation states presented here.

  19. Americium characterization by X-ray fluorescence and absorption spectroscopy in plutonium uranium mixed oxide

    SciTech Connect

    Degueldre, Claude Cozzo, Cedric; Martin, Matthias; Grolimund, Daniel; Mieszczynski, Cyprian

    2013-06-01

    Plutonium uranium mixed oxide (MOX) fuels are currently used in nuclear reactors. The actinides in these fuels need to be analyzed after irradiation for assessing their behaviour with regard to their environment and the coolant. In this work the study of the atomic structure and next-neighbour environment of Am in the (Pu,U)O₂ lattice in an irradiated (60 MW d kg⁻¹) MOX sample was performed employing micro-X-ray fluorescence (µ-XRF) and micro-X-ray absorption fine structure (µ-XAFS) spectroscopy. The chemical bonds, valences and stoichiometry of Am (~0.66 wt%) are determined from the experimental data gained for the irradiated fuel material examined in its peripheral zone (rim) of the fuel. In the irradiated sample Am builds up as Am³⁺ species within an [AmO₈]¹³⁻ coordination environment (e.g. >90%) and no (<10%) Am(IV) or (V) can be detected in the rim zone. The occurrence of americium dioxide is avoided by the redox buffering activity of the uranium dioxide matrix. - Graphical abstract: Americium LIII XAFS spectra recorded for the irradiated MOX sub-sample in the rim zone for a 300 μm×300 μm beam size area investigated over six scans of 4 h. The records remain constant during multi-scan. The analysis of the XAFS signal shows that Am is found as trivalent in the UO₂ matrix. This analytical work shall open the door of very challenging analysis (speciation of fission product and actinides) in irradiated nuclear fuels. - Highlights: • Americium was characterized by microX-ray absorption spectroscopy in irradiated MOX fuel. • The americium redox state as determined from XAS data of irradiated fuel material was Am(III). • In the sample, the Am³⁺ face an AmO₈¹³⁻coordination environment in the (Pu,U)O₂ matrix. • The americium dioxide is reduced by the uranium dioxide matrix.

  20. Laboratory absorption spectra of molecules at interstellar cloud temperatures - First measurements on CO at about 97 nm

    NASA Technical Reports Server (NTRS)

    Smith, P. L.; Yoshino, K.; Stark, G.; Ito, K.; Stevens, M. H.

    1991-01-01

    In the 91-100 nm spectral region, where absorption of photons by interstellar CO usually leads to dissociation, laboratory spectra obtained at 295 K show that most CO bands are both overlapped and perturbed. Reliable band oscillator strengths cannot be extracted from such spectra. As a consequence, synthetic extreme-ultraviolet absorption spectra for CO at the low temperatures that prevail in interstellar clouds are uncertain. A supersonic expansion technique has been used to cool CO to 30 K and three bands in the 97-nm region have been studied with high spectral resolution. The measured spectrum at 30 K is in reasonable agreement with some published modeled spectra, but the ratios of integrated cross sections are somewhat different from those determined from low resolution spectra obtained at 295 K, in which the bands are blended.

  1. Absorption and Fluorescence Properties of Chromophoric Dissolved Organic Matter Produced by Algae.

    PubMed

    Peng, Tong; Lu, Xiao-lan; Su, Rong-guo; Zhang, Dong-mei

    2015-09-01

    Four kinds of diatom (Chaetoceros curvisetus, Phaeodactylum tricornutum, Nitzschia closterium f. minutissima and Navicula halophile) and two kinds of dinoflagellates (Prorocentrum donghaiense and Gymnodinium) were cultured under laboratory conditions. Variations of optical properties of chromophoric dissolved organic matter (CDOM) were studied with absorption and fluorescence excitation-emission matrix spectroscopy(EEM) during growth of marine microalgae in incubation experiment. Absorption spectrum revealed absorption coefficient a(355) (CDOM absorption coefficients at 355 nm) of 6 kinds of marine microalgae above increased by 64.8%, 242.3%, 535.1%, 903.2%, 836% and 196.4%, respectively. Simultaneously, the absorption spectral slope (Sg), determined between 270 and 350 nm, representing the size of molecular weight of CDOM and humic-like composition, decreased by 8.7%, 34.6%, 39.4%, 53.1%, 46.7%, and 35.7%, respectively. Applying parallel factor analysis (PARAFAC) together with EEM got four components of CDOM: C1(Ex/Em=350(260) nm/450 nm), C2 (Ex/Em=260(430) nm/525 nm), C3 (Ex/Em=325 nm/400 nm) and C4(Ex/Em=275 nm/325 nm), which were relative to three humic-like and one protein-like fluorescent components of Nitzschia closterium f. minutissima and Navicula halophile. In incubation experiment, fluorescence intensity of these four components during growth of Nitzschia closterium f. minutissima increased by, respectively, 8.68, 24.9, 7.19 and 39.8 times, and those of Navicula halophile increased by 2.64, 0.07, 4.39 and 12.4 times, respectively. Significant relationships were found between the fluorescence intensity of four components of CDOM, a(355) and Sg. All results demonstrated that both content and molecular weight of CDOM produced by diatom and dinoflagellate studied in incubation experiment increased, but these two parameters changed more obviously of the diatom than those of dinoflagellate; the proportion of humic-like components in the composition of CDOM

  2. Absorption and Fluorescence Properties of Chromophoric Dissolved Organic Matter Produced by Algae.

    PubMed

    Peng, Tong; Lu, Xiao-lan; Su, Rong-guo; Zhang, Dong-mei

    2015-09-01

    Four kinds of diatom (Chaetoceros curvisetus, Phaeodactylum tricornutum, Nitzschia closterium f. minutissima and Navicula halophile) and two kinds of dinoflagellates (Prorocentrum donghaiense and Gymnodinium) were cultured under laboratory conditions. Variations of optical properties of chromophoric dissolved organic matter (CDOM) were studied with absorption and fluorescence excitation-emission matrix spectroscopy(EEM) during growth of marine microalgae in incubation experiment. Absorption spectrum revealed absorption coefficient a(355) (CDOM absorption coefficients at 355 nm) of 6 kinds of marine microalgae above increased by 64.8%, 242.3%, 535.1%, 903.2%, 836% and 196.4%, respectively. Simultaneously, the absorption spectral slope (Sg), determined between 270 and 350 nm, representing the size of molecular weight of CDOM and humic-like composition, decreased by 8.7%, 34.6%, 39.4%, 53.1%, 46.7%, and 35.7%, respectively. Applying parallel factor analysis (PARAFAC) together with EEM got four components of CDOM: C1(Ex/Em=350(260) nm/450 nm), C2 (Ex/Em=260(430) nm/525 nm), C3 (Ex/Em=325 nm/400 nm) and C4(Ex/Em=275 nm/325 nm), which were relative to three humic-like and one protein-like fluorescent components of Nitzschia closterium f. minutissima and Navicula halophile. In incubation experiment, fluorescence intensity of these four components during growth of Nitzschia closterium f. minutissima increased by, respectively, 8.68, 24.9, 7.19 and 39.8 times, and those of Navicula halophile increased by 2.64, 0.07, 4.39 and 12.4 times, respectively. Significant relationships were found between the fluorescence intensity of four components of CDOM, a(355) and Sg. All results demonstrated that both content and molecular weight of CDOM produced by diatom and dinoflagellate studied in incubation experiment increased, but these two parameters changed more obviously of the diatom than those of dinoflagellate; the proportion of humic-like components in the composition of CDOM

  3. Constraints on Reionization and Source Properties from the Absorption Spectra of z > 6.2 Quasars

    NASA Astrophysics Data System (ADS)

    Mesinger, Andrei; Haiman, Zoltán

    2007-05-01

    We make use of hydrodynamical simulations of the intergalactic medium (IGM) to create model quasar absorption spectra. We compare these model spectra with the observed Keck spectra of three z>6.2 quasars with full Gunn-Peterson troughs: SDSS J1148+5251 (z=6.42), SDSS J1030+0524 (z=6.28), and SDSS J1623+3112 (z=6.22). We fit the probability density distributions (PDFs) of the observed Lyα optical depths (τα) with those generated from the simulation by exploring a range of values for the size of the quasar's surrounding H II region, RS; the volume-weighted mean neutral hydrogen fraction in the ambient IGM, x¯HI; and the quasar's ionizing photon emissivity, N˙Q. In order to avoid averaging over possibly large sight line-to-sight line fluctuations in IGM properties, we analyze each observed quasar independently. We find the following results for J1148+5251, J1030+0524, and J1623+3112: the best-fit sizes RS are 40, 41, and 29 (comoving) Mpc, respectively. For the later two quasars, the value is significantly larger than the radius corresponding to the wavelength at which the quasar's flux vanishes. These constraints are tight, with only ~10% uncertainties, comparable to those caused by redshift determination errors. The best-fit values of N˙Q are 2.1, 1.3, and 0.9×1057 s-1, respectively, with a factor of ~2 uncertainty in each case. Finally, the best-fit values of x¯HI are 0.16, 1.0, and 1.0, respectively. The uncertainty in the case of J1148+5251 is large, and x¯HI is not well constrained. However, for both J1030+0524 and J1623+3112, we find a significant lower limit of x¯HI>~0.033. Our method is different from previous analyses of the GP absorption spectra of these quasars, and our results strengthen the evidence that the rapid end stage of reionization is occurring near z~6.

  4. Simulation of X-ray absorption spectra with orthogonality constrained density functional theory†

    PubMed Central

    Derricotte, Wallace D.; Evangelista, Francesco A.

    2015-01-01

    Orthogonality constrained density functional theory (OCDFT) is a variational time-independent approach for the computation of electronic excited states. In this work we extend OCDFT to compute core-excited states and generalize the original formalism to determine multiple excited states. Benchmark computations on a set of 13 small molecules and 40 excited states show that unshifted OCDFT/B3LYP excitation energies have a mean absolute error of 1.0 eV. Contrary to time-dependent DFT, OCDFT excitation energies for first- and second-row elements are computed with near-uniform accuracy. OCDFT core excitation energies are insensitive to the choice of the functional and the amount of Hartree–Fock exchange. We show that OCDFT is a powerful tool for the assignment of X-ray absorption spectra of large molecules by simulating the gas-phase near-edge spectrum of adenine and thymine. PMID:25690350

  5. Electronic absorption spectra of linear and cyclic Cn+ n=7-9 in a neon matrix

    NASA Astrophysics Data System (ADS)

    Fulara, Jan; Shnitko, Ivan; Batalov, Anton; Maier, John P.

    2005-07-01

    The Cn+n=7-9 cations were produced by electron-impact ionization of perchloronaphthalene, mass selected, and their electronic absorption spectra in 6K neon matrices recorded. The linear and cyclic isomers of C7+ and C8+ are detected. Three systems of linear C7+ are observed with origin bands near 770, 332, and 309nm. The cyclic C7+ shows two transitions near 676 and 448nm. One system of linear C9+ is observed commencing at 371nm. Linear C8+ shows five dipole-allowed electronic transitions from the X˜Πg2 ground state, and the strongest ones have the origin bands at 890.8 and 308.1nm. Five electronic transitions of cyclic C8+ are also discernible.

  6. Error reduction in retrievals of atmospheric species from symmetrically measured lidar sounding absorption spectra.

    PubMed

    Chen, Jeffrey R; Numata, Kenji; Wu, Stewart T

    2014-10-20

    We report new methods for retrieving atmospheric constituents from symmetrically-measured lidar-sounding absorption spectra. The forward model accounts for laser line-center frequency noise and broadened line-shape, and is essentially linearized by linking estimated optical-depths to the mixing ratios. Errors from the spectral distortion and laser frequency drift are substantially reduced by averaging optical-depths at each pair of symmetric wavelength channels. Retrieval errors from measurement noise and model bias are analyzed parametrically and numerically for multiple atmospheric layers, to provide deeper insight. Errors from surface height and reflectance variations are reduced to tolerable levels by "averaging before log" with pulse-by-pulse ranging knowledge incorporated.

  7. kspectrum: an open-source code for high-resolution molecular absorption spectra production

    NASA Astrophysics Data System (ADS)

    Eymet, V.; Coustet, C.; Piaud, B.

    2016-01-01

    We present the kspectrum, scientific code that produces high-resolution synthetic absorption spectra from public molecular transition parameters databases. This code was originally required by the atmospheric and astrophysics communities, and its evolution is now driven by new scientific projects among the user community. Since it was designed without any optimization that would be specific to any particular application field, its use could also be extended to other domains. kspectrum produces spectral data that can subsequently be used either for high-resolution radiative transfer simulations, or for producing statistic spectral model parameters using additional tools. This is a open project that aims at providing an up-to-date tool that takes advantage of modern computational hardware and recent parallelization libraries. It is currently provided by Méso-Star (http://www.meso-star.com) under the CeCILL license, and benefits from regular updates and improvements.

  8. Optical absorption and energy-loss spectra of aligned carbon nanotubes

    NASA Astrophysics Data System (ADS)

    García-Vidal, F. J.; Pitarke, J. M.

    2001-07-01

    Optical-absorption cross-sections and energy-loss spectra of aligned multishell carbon nanotubes are investigated, on the basis of photonic band-structure calculations. A local graphite-like dielectric tensor is assigned to every point of the tubules, and the effective transverse dielectric function of the composite is computed by solving Maxwell's equations in media with tensor-like dielectric functions. A Maxwell-Garnett-like approach appropriate to the case of infinitely long anisotropic tubules is also developed. Our full calculations indicate that the experimentally measured macroscopic dielectric function of carbon nanotube materials is the result of a strong electromagnetic coupling between the tubes. An analysis of the electric-field pattern associated with this coupling is presented, showing that in the close-packed regime the incident radiation excites a very localized tangential surface plasmon.

  9. Detection of cervical cancer by fluorescence emission and stokes' shift spectra of blood and urine

    NASA Astrophysics Data System (ADS)

    Masilamani, V.; Vijmasi, T.; AlSalhi, M.; Govindarajan, K.; VijayaRaghavan, A. P.; Rai, Ram Rathan

    2011-03-01

    In this paper we present the results of a study to distinguish cervical cancer patients [ N=50] from healthy subjects [N=50] based on the Fluorescence Emission Spectra [FES] and Stokes' Shift Spectra [SSS] of blood and urine. FES was obtained from the cellular fraction of blood and urine by excitation at 400 nm. SSS was obtained from blood plasma and urine with Δλ of 70nm. In the FES of blood cellular fraction, the ratio of intensity of the two bands due to neutral porphyrin and basic porphyrin [I630 / I580] was 1 for normal controls and 3 for cervical cancers. In the SSS of plasma, the average ratio of intensity of the two bands due to tryptophan and collagen [I305 nm / I340 nm] was 1.9 for normal controls, 1.1 for early cervical cancers and 0.9 for advanced cervical cancers In the SSS of urine, the ratio of intensity of the two bands due to flavin and NADH [I450 nm / I360 nm] was 0.2 for normal controls and 0.8 for cancer patients. A discriminant analysis combining all three parameters showed a sensitivity of 80% and specificity of 78% for this technique. In this study we show that fluorescence spectroscopy of blood and urine could develop into a promising technique for non-invasive diagnosis and screening of cervical cancers and would appropriately supplement or complement currently used techniques.

  10. Absorption spectrophotometric, fluorescence, transient absorption and quantum chemical investigations on fullerene/phthalocyanine supramolecular complexes.

    PubMed

    Ray, Anamika; Santhosh, Kotni; Bhattacharya, Sumanta

    2011-05-01

    The present paper reports the photophysical investigations on supramolecular interaction of a phthalocyanine derivative, namely, 2,9,16,23-tetra-tert-butyl-29H,31H-Pc (1) with C(60) and C(70) in toluene. The binding constants of the C(60) and C(70) complexes of 1 are estimated to be 27,360 and 25,205 dm(3), respectively. Transient absorption measurements in the visible region establishes that energy transfer from C60*T (and C70*T) to 1 occurs predominantly in toluene which is subsequently confirmed by the consecutive appearance of the triplet states of 1. Quantum chemical calculations at DFT level of theory explore the geometry and electronic structure of the supramolecules and testify the significant redistribution of charge between fullerenes and 1.

  11. Synthesis, Characterization, Absorption Spectra, and Luminescence Properties of Organometallic Platinum(II) Terpyridine Complexes.

    PubMed

    Arena, Giuseppe; Calogero, Giuseppe; Campagna, Sebastiano; Monsù Scolaro, Luigi; Ricevuto, Vittorio; Romeo, Raffaello

    1998-06-01

    A series of new organometallic platinum(II) complexes containing terdentate polypyridine ligands has been prepared and characterized. Their absorption spectra in 4:1 (v/v) MeOH/EtOH fluid solution at room temperature and luminescence in the same matrix at 77 K have been investigated. The new species are [Pt(terpy)Ph]Cl (3, terpy = 2,2':6',2"-terpyridine, Ph = phenyl), [Pt(Ph-terpy)Cl]Cl (4, Ph-terpy = 4'-phenyl-2,2':6',2"-terpyridine), [Pt(Ph-terpy)Me]Cl (5), and [Pt(Ph-terpy)Ph]Cl (6). The results have been compared with those for [Pt(terpy)Cl]Cl (1) and [Pt(terpy)Me]Cl (2). NMR data evidence that all the complexes but 3 and 6 oligomerize in solution leading to stacked species. The absorption spectra are dominated by moderately intense metal-to-ligand charge-transfer (MLCT) bands in the visible region and by intense ligand-centered (LC) bands in the UV region. All the compounds are luminescent in a 4:1 (v/v) MeOH/EtOH rigid matrix at 77 K, exhibiting a structured emission within the range 460-600 nm. This feature is assigned to formally (3)LC excited states which receive substantial contribution from closely lying (3)MLCT levels. Complexes 1, 2, 4, and 5 also exhibit a relatively narrow and unstructured luminescence band within the range 680-800 nm, which dominates the luminescence spectrum on increasing concentration and exciting at longer wavelengths. The band is assigned to a dsigma(metal) --> pi(polypyridine) ((3)MMLCT) state, originating from metal-metal interactions occurring in head-to-tail dimers (or polymers). A third broad band is shown by 1 and 4 under all concentration conditions and by 2 and 5 only in concentrated solutions and is attributed to excimeric species originating from pi-pi interactions due to stacking between polypyridine ligands.

  12. VARIABILITY OF WATER AND OXYGEN ABSORPTION BANDS IN THE DISK-INTEGRATED SPECTRA OF EARTH

    SciTech Connect

    Fujii, Yuka; Suto, Yasushi; Turner, Edwin L.

    2013-03-10

    We study the variability of major atmospheric absorption features in the disk-integrated spectra of Earth with future application to Earth-analogs in mind, concentrating on the diurnal timescale. We first analyze observations of Earth provided by the EPOXI mission, and find 5%-20% fractional variation of the absorption depths of H{sub 2}O and O{sub 2} bands, two molecules that have major signatures in the observed range. From a correlation analysis with the cloud map data from the Earth Observing Satellite (EOS), we find that their variation pattern is primarily due to the uneven cloud cover distribution. In order to account for the observed variation quantitatively, we consider a simple opaque cloud model, which assumes that the clouds totally block the spectral influence of the atmosphere below the cloud layer, equivalent to assuming that the incident light is completely scattered at the cloud top level. The model is reasonably successful, and reproduces the EPOXI data from the pixel-level EOS cloud/water vapor data. A difference in the diurnal variability patterns of H{sub 2}O and O{sub 2} bands is ascribed to the differing vertical and horizontal distribution of those molecular species in the atmosphere. On Earth, the inhomogeneous distribution of atmospheric water vapor is due to the existence of its exchange with liquid and solid phases of H{sub 2}O on the planet's surface on a timescale short compared with atmospheric mixing times. If such differences in variability patterns were detected in spectra of Earth-analogs, it would provide the information on the inhomogeneous composition of their atmospheres.

  13. Estimation of Biological Oxygen Demand and Chemical Oxygen Demand for Combined Sewer Systems Using Synchronous Fluorescence Spectra

    PubMed Central

    Hur, Jin; Lee, Bo-Mi; Lee, Tae-Hwan; Park, Dae-Hee

    2010-01-01

    Real-time monitoring of water quality for sewer system is required for efficient sewer network design because it provides information on the precise loading of pollutant to wastewater treatment facilities and the impact of loading on receiving water. In this study, synchronous fluorescence spectra and its first derivatives were investigated using a number of wastewater samples collected in sewer systems in urban and non-urban areas, and the optimum fluorescence feature was explored for the estimation of biochemical oxygen demand (BOD) and chemical oxygen demand (COD) concentrations of sewer samples. The temporal variations in BOD and COD showed a regular pattern for urban areas whereas they were relatively irregular for non-urban areas. Irrespective of the sewer pipes and the types of the areas, two distinct peaks were identified from the synchronous fluorescence spectra, which correspond to protein-like fluorescence (PLF) and humic-like fluorescence (HLF), respectively. HLF in sewer samples appears to be associated with fluorescent whitening agents. Five fluorescence characteristics were selected from the synchronous spectra and the first-derivatives. Among the selected fluorescence indices, a peak in the PLF region (i.e., Index I) showed the highest correlation coefficient with both BOD and COD. A multiple regression approach based on suspended solid (SS) and Index I used to compensate for the contribution of SS to BOD and COD revealed an improvement in the estimation capability, showing good correlation coefficients of 0.92 and 0.94 for BOD and COD, respectively. PMID:22319257

  14. Estimation of biological oxygen demand and chemical oxygen demand for combined sewer systems using synchronous fluorescence spectra.

    PubMed

    Hur, Jin; Lee, Bo-Mi; Lee, Tae-Hwan; Park, Dae-Hee

    2010-01-01

    Real-time monitoring of water quality for sewer system is required for efficient sewer network design because it provides information on the precise loading of pollutant to wastewater treatment facilities and the impact of loading on receiving water. In this study, synchronous fluorescence spectra and its first derivatives were investigated using a number of wastewater samples collected in sewer systems in urban and non-urban areas, and the optimum fluorescence feature was explored for the estimation of biochemical oxygen demand (BOD) and chemical oxygen demand (COD) concentrations of sewer samples. The temporal variations in BOD and COD showed a regular pattern for urban areas whereas they were relatively irregular for non-urban areas. Irrespective of the sewer pipes and the types of the areas, two distinct peaks were identified from the synchronous fluorescence spectra, which correspond to protein-like fluorescence (PLF) and humic-like fluorescence (HLF), respectively. HLF in sewer samples appears to be associated with fluorescent whitening agents. Five fluorescence characteristics were selected from the synchronous spectra and the first-derivatives. Among the selected fluorescence indices, a peak in the PLF region (i.e., Index I) showed the highest correlation coefficient with both BOD and COD. A multiple regression approach based on suspended solid (SS) and Index I used to compensate for the contribution of SS to BOD and COD revealed an improvement in the estimation capability, showing good correlation coefficients of 0.92 and 0.94 for BOD and COD, respectively.

  15. Mathematical model to interpret localized reflectance spectra measured in the presence of a strong fluorescence marker.

    PubMed

    Bravo, Jaime J; Davis, Scott C; Roberts, David W; Paulsen, Keith D; Kanick, Stephen C

    2016-06-01

    Quantification of multiple fluorescence markers during neurosurgery has the potential to provide complementary contrast mechanisms between normal and malignant tissues, and one potential combination involves fluorescein sodium (FS) and aminolevulinic acid-induced protoporphyrin IX (PpIX). We focus on the interpretation of reflectance spectra containing contributions from elastically scattered (reflected) photons as well as fluorescence emissions from a strong fluorophore (i.e., FS). A model-based approach to extract μa and μ′s in the presence of FS emission is validated in optical phantoms constructed with Intralipid (1% to 2% lipid) and whole blood (1% to 3% volume fraction), over a wide range of FS concentrations (0 to 1000  μg/ml 1000  μg/ml ). The results show that modeling reflectance as a combination of elastically scattered light and attenuation-corrected FS-based emission yielded more accurate tissue parameter estimates when compared with a nonmodified reflectance model, with reduced maximum errors for blood volume (22% versus 90%), microvascular saturation (21% versus 100%), and μs′ (13% versus 207%). Additionally, quantitative PpIX fluorescence sampled in the same phantom as FS showed significant differences depending on the reflectance model used to estimate optical properties (i.e., maximum error 29% versus 86%). These data represent a first step toward using quantitative optical spectroscopy to guide surgeries through simultaneous assessment of FS and PpIX. PMID:26836297

  16. Modeling structure and spectra of the kindling fluorescent protein asFP595

    NASA Astrophysics Data System (ADS)

    Collins, Jack R.; Topol, Igor A.; Savitsky, Alexander P.; Nemukhin, Alexander V.

    2011-03-01

    Modern computational approaches based on quantum mechanical methods to characterize structures and optical spectra of biological chromophores in proteins are intensively used to gain knowledge of events occurring upon of their photoexcitation. Primary attention is paid to the species from the family of the green fluorescent protein applied as biomarkers in living cells. We apply quantum chemical approaches for accurate calculations of the structures of the chromophore binding pockets and to estimate spectral bands corresponding to the S0-S1 optical transitions of the intriguing kindling protein asFP595. Its precursor, the chromoprotein asCP from the sea anemony Anemonia sulcata is characterized by distinctive spectral properties: at low light intensities the wild-type protein is weakly fluorescent with the very low quantum yield, however, high intensity irradiation with green light leads to a drastic increase of quantum yield. This phenomenon is now termed "kindling". In simulations, the model system is designed as a molecular cluster constructed on the basis of available crystal structures of the related protein. The equilibrium geometry of the cluster is optimized using density functional theory approximations. The vertical excitation energies corresponding to the S0-S1 transitions are computed by using the semiempirical ZINDO technique. A special attention is paid to evaluate effects of point mutations in the vicinity of the chromophore group. Theoretical data provide important information on the chromophore properties aiming to interpret the results of experimental studies and applications of this fluorescent protein.

  17. Mathematical model to interpret localized reflectance spectra measured in the presence of a strong fluorescence marker

    NASA Astrophysics Data System (ADS)

    Bravo, Jaime J.; Davis, Scott C.; Roberts, David W.; Paulsen, Keith D.; Kanick, Stephen C.

    2016-06-01

    Quantification of multiple fluorescence markers during neurosurgery has the potential to provide complementary contrast mechanisms between normal and malignant tissues, and one potential combination involves fluorescein sodium (FS) and aminolevulinic acid-induced protoporphyrin IX (PpIX). We focus on the interpretation of reflectance spectra containing contributions from elastically scattered (reflected) photons as well as fluorescence emissions from a strong fluorophore (i.e., FS). A model-based approach to extract μa and μs‧ in the presence of FS emission is validated in optical phantoms constructed with Intralipid (1% to 2% lipid) and whole blood (1% to 3% volume fraction), over a wide range of FS concentrations (0 to 1000 μg/ml). The results show that modeling reflectance as a combination of elastically scattered light and attenuation-corrected FS-based emission yielded more accurate tissue parameter estimates when compared with a nonmodified reflectance model, with reduced maximum errors for blood volume (22% versus 90%), microvascular saturation (21% versus 100%), and μs‧ (13% versus 207%). Additionally, quantitative PpIX fluorescence sampled in the same phantom as FS showed significant differences depending on the reflectance model used to estimate optical properties (i.e., maximum error 29% versus 86%). These data represent a first step toward using quantitative optical spectroscopy to guide surgeries through simultaneous assessment of FS and PpIX.

  18. Size control of semimetal bismuth nanoparticles and the UV-visible and IR absorption spectra.

    PubMed

    Wang, Y W; Hong, Byung Hee; Kim, Kwang S

    2005-04-21

    We introduced a simple chemical method to synthesize semimetal bismuth nanoparticles in N,N-dimethylformamide (DMF) by reducing Bi(3+) with sodium borohydride (NaBH(4)) in the presence of poly(vinylpyrroldone) (PVP) at room temperature. The size and dispersibility of Bi nanoparticles can be easily controlled by changing the synthetic conditions such as the molar ratio of PVP to BiCl(3) and the concentration of BiCl(3). The UV-visible absorption spectra of Bi nanoparticles of different diameters are systematically studied. The surface plasmon peaks broaden with the increasing molar ratio of PVP to BiCl(3) as the size of bismuth nanoparticles decreases. Infrared (IR) spectra of the complexes with different molar ratios of PVP/BiCl(3) show a strong interaction between the carboxyl oxygen (C=O) of PVP and Bi(3+) ion and a weak interaction between the carboxyl oxygen (C=O) of PVP and the Bi atom in nanoparticles. This indicates that PVP serves as an effective capping ligand, which prevents the nanoparticles from aggregation.

  19. Investigation of absorption spectra of Gafchromic EBT2 film's components and their impact on UVR dosimetry

    NASA Astrophysics Data System (ADS)

    Aydarous, Abdulkadir

    2016-05-01

    The absorption spectra of the EBT2 film's components were investigated in conjunction with its use for UVA dosimetry. The polyester (topside) and adhesive layers of the EBT2 film have been gently removed. Gafchromic™ EBT2 films with and without the protected layers (polyester and adhesive) were exposed to UVR of 365 nm for different durations. Thereafter, the UV-visible spectra were measured using a UV-visible spectrophotometer (Model Spectro Dual Split Beam, UVS-2700). Films were digitized using a Nikon CanoScan 9000F Mark II flatbed scanner. The dosimetric characteristics including film's uniformity, reproducibility and post-irradiation development were investigated. The color development of EBT2 and new modified EBT2 (EBT2-M) films irradiated with UVA was relatively stable (less than 1%) immediately after exposure. Based on this study, the sensitivity of EBT2 to UVR with wavelength between ~350 nm and ~390 nm can significantly be enhanced if the adhesive layer (~25 μm) is removed. The polyester layer plays almost no part on absorbing UVR with wavelength between ~320 nm and ~390 nm. Furthermore, various sensitivities for the EBT2-M film has been established depending on the wavelength of analysis.

  20. Total Absorption Spectroscopy of Fission Fragments Relevant for Reactor Antineutrino Spectra and Decay Heat Calculations

    NASA Astrophysics Data System (ADS)

    Porta, A.; Zakari-Issoufou, A.-A.; Fallot, M.; Algora, A.; Tain, J. L.; Valencia, E.; Rice, S.; Bui, V. M.; Cormon, S.; Estienne, M.; Agramunt, J.; Äystö, J.; Bowry, M.; Briz, J. A.; Caballero-Folch, R.; Cano-Ott, D.; Cucouanes, A.; Elomaa, V.-V.; Eronen, T.; Estévez, E.; Farrelly, G. F.; Garcia, A. R.; Gelletly, W.; Gomez-Hornillos, M. B.; Gorlychev, V.; Hakala, J.; Jokinen, A.; Jordan, M. D.; Kankainen, A.; Karvonen, P.; Kolhinen, V. S.; Kondev, F. G.; Martinez, T.; Mendoza, E.; Molina, F.; Moore, I.; Perez-Cerdán, A. B.; Podolyák, Zs.; Penttilä, H.; Regan, P. H.; Reponen, M.; Rissanen, J.; Rubio, B.; Shiba, T.; Sonzogni, A. A.; Weber, C.

    2016-03-01

    Beta decay of fission products is at the origin of decay heat and antineutrino emission in nuclear reactors. Decay heat represents about 7% of the reactor power during operation and strongly impacts reactor safety. Reactor antineutrino detection is used in several fundamental neutrino physics experiments and it can also be used for reactor monitoring and non-proliferation purposes. 92,93Rb are two fission products of importance in reactor antineutrino spectra and decay heat, but their β-decay properties are not well known. New measurements of 92,93Rb β-decay properties have been performed at the IGISOL facility (Jyväskylä, Finland) using Total Absorption Spectroscopy (TAS). TAS is complementary to techniques based on Germanium detectors. It implies the use of a calorimeter to measure the total gamma intensity de-exciting each level in the daughter nucleus providing a direct measurement of the beta feeding. In these proceedings we present preliminary results for 93Rb, our measured beta feedings for 92Rb and we show the impact of these results on reactor antineutrino spectra and decay heat calculations.

  1. Source brightness fluctuation correction of solar absorption fourier transform mid infrared spectra

    NASA Astrophysics Data System (ADS)

    Ridder, T.; Warneke, T.; Notholt, J.

    2011-06-01

    The precision and accuracy of trace gas observations using solar absorption Fourier Transform infrared spectrometry depend on the stability of the light source. Fluctuations in the source brightness, however, cannot always be avoided. Current correction schemes, which calculate a corrected interferogram as the ratio of the raw DC interferogram and a smoothed DC interferogram, are applicable only to near infrared measurements. Spectra in the mid infrared spectral region below 2000 cm-1 are generally considered uncorrectable, if they are measured with a MCT detector. Such measurements introduce an unknown offset to MCT interferograms, which prevents the established source brightness fluctuation correction. This problem can be overcome by a determination of the offset using the modulation efficiency of the instrument. With known modulation efficiency the offset can be calculated, and the source brightness correction can be performed on the basis of offset-corrected interferograms. We present a source brightness fluctuation correction method which performs the smoothing of the raw DC interferogram in the interferogram domain by an application of a running mean instead of high-pass filtering the corresponding spectrum after Fourier transformation of the raw DC interferogram. This smoothing can be performed with the onboard software of commercial instruments. The improvement of MCT spectra and subsequent ozone profile and total column retrievals is demonstrated. Application to InSb interferograms in the near infrared spectral region proves the equivalence with the established correction scheme.

  2. Change in the absorption spectra of blood exposed to a low-frequency magnetic field

    NASA Astrophysics Data System (ADS)

    Zalesskaya, G. A.; Mit'kovskaya, N. P.; Galai, O. A.; Kuchinskii, A. V.; Laskina, O. V.

    2007-03-01

    We have used the absorption spectra of whole blood in the UV-visible and IR regions of the spectrum to study changes in the structure of the molecular components of blood when exposed to a low-frequency pulsed magnetic field used to treat ischemic heart disease. We show that pronounced changes in the spectra when the blood is directly exposed in vivo to a magnetic field may be due to breaking of the bond between the heme group and the protein of the hemoglobin, as a consequence of changes in the intermolecular interactions in the polypeptide chains of the hemoglobin and also the spin states of the paramagnetic heme components. Exposure to a magnetic field results in changes in the conformations of the polypeptide chains of hemoglobin and the rate of dissociation of oxyhemoglobin. The structural changes in the hemoglobin molecule are considered as one of the possible primary mechanisms of action on blood in vivo for a low-frequency pulsed magnetic field.

  3. DFT study of the effect of substituents on the absorption and emission spectra of Indigo

    PubMed Central

    2012-01-01

    Background Theoretical analyses of the indigo dye molecule and its derivatives with Chlorine (Cl), Sulfur (S), Selenium (Se) and Bromine (Br) substituents, as well as an analysis of the Hemi-Indigo molecule, were performed using the Gaussian 03 software package. Results Calculations were performed based on the framework of density functional theory (DFT) with the Becke 3- parameter-Lee-Yang-Parr (B3LYP) functional, where the 6-31 G(d,p) basis set was employed. The configuration interaction singles (CIS) method with the same basis set was employed for the analysis of excited states and for the acquisition of the emission spectra. Conclusions The presented absorption and emission spectra were affected by the substitution position. When a hydrogen atom of the molecule was substituted by Cl or Br, practically no change in the absorbed and emitted energies relative to those of the indigo molecule were observed; however, when N was substituted by S or Se, the absorbed and emitted energies increased. PMID:22809100

  4. Linewidth Extraction From the THz Absorption Spectra Using a Modified Lorentz Model

    NASA Astrophysics Data System (ADS)

    Li, Zhi; Zhang, Zhaohui; Zhao, Xiaoyan; Su, Haixia; Zhang, Han; Lan, Jinhui

    2013-10-01

    Identification of specific materials is one of the most promising THz applications. It is commonly achieved by comparing the experimental peak central frequencies of the transmission or absorption spectra with a database for known materials while neglecting the linewidths. However, due to the restriction of the signal-to-noise ratio, only a narrow band, extending from several hundred GHz to several THz, can be used. It is difficult to distinguish two materials from each other if their peaks' central frequencies are similar. In this paper, we present a modified Lorentz model by taking the scattering effect into account. The modified Lorentz model can be used for the extraction of reliable absorption peak parameters, i.e. the central frequency and linewidth. On comparison with our experiments, we observed that the parameters extracted using the modified Lorentz model in glutamine samples of different concentrations exhibited a better agreement than those obtained using the traditional model. Therefore, the utilization of the narrow THz band to identify materials can be improved by comparing both the central frequency and linewidth obtained from this method.

  5. Absorption spectra of isomeric OH adducts of 1,3,7-trimethylxanthine

    SciTech Connect

    Vinchurkar, M.S.; Rao, B.S.M.; Mohan, H.; Mittal, J.P.; Schmidt, K.H.; Jonah, C.D.

    1997-04-17

    The reactions of OH{sup .}, O{sup .-}, and SO{sub 4}{sup .-} with 1,3,7-trimethylxanthine (caffeine) were studied by pulse radiolysis with optical and conductance detection techniques. The absorption spectra of transients formed in OH{sup .} reaction in neutral solutions exhibited peaks at 310 and 335 nm, as well as a broad absorption maximum at 500 nm, which decayed by first-order kinetics. The rate (k = (4.0 {+-} 0.5) x 10{sup 4} s{sup -1}) of this decay is independent of pH in the range 4-9 and is in agreement with that determined from the conductance detection (k = 4 x 10{sup 4} s{sup -1}). The spectrum in acidic solutions has only a broad peak around 330 nm with no absorption in the higher wavelength region. The intermediates formed in reaction of O{sup .-} absorb around 310 and at 350 nm, and the first-order decay at the latter wavelength was not seen. The OH radical adds to C-4 (X-40H{sup .}) and C-8 (X-80H{sup .}) positions of caffeine in the ratio 1:2 as determined from the redox titration and conductivity measurements. H abstraction from the methyl group is an additional reaction channel in O{sup .-} reaction. Dehydroxylation of the X-40H{sup .} adduct occurs, whereas the X-80H{sup .} adduct does not undergo ring opening. The spectrum obtained for OH{sup .} reaction in oxygenated solutions is similar to that observed in SO{sub 4}{sup .-} reaction in basic solutions. 25 refs., 5 figs., 1 tab.

  6. Absorption spectra and photolysis of methyl peroxide in liquid and frozen water.

    PubMed

    Epstein, Scott A; Shemesh, Dorit; Tran, Van T; Nizkorodov, Sergey A; Gerber, R Benny

    2012-06-21

    Methyl peroxide (CH(3)OOH) is commonly found in atmospheric waters and ices in significant concentrations. It is the simplest organic peroxide and an important precursor to hydroxyl radical. Many studies have examined the photochemical behavior of gaseous CH(3)OOH; however, the photochemistry of liquid and frozen water solutions is poorly understood. We present a series of experiments and theoretical calculations designed to elucidate the photochemical behavior of CH(3)OOH dissolved in liquid water and ice over a range of temperatures. The molar extinction coefficients of aqueous CH(3)OOH are different from the gas phase, and they do not change upon freezing. Between -12 and 43 °C, the quantum yield of CH(3)OOH photolysis is described by the following equation: Φ(T) = exp((-2175 ± 448)1/T) + 7.66 ± 1.56). We use on-the-fly ab initio molecular dynamics simulations to model structures and absorption spectra of a bare CH(3)OOH molecule and a CH(3)OOH molecule immersed inside 20 water molecules at 50, 200, and 220 K. The simulations predict large sensitivity in the absorption spectrum of CH(3)OOH to temperature, with the spectrum narrowing and shifting to the blue under cryogenic conditions because of constrained dihedral motion around the O-O bond. The shift in the absorption spectrum is not observed in the experiment when the CH(3)OOH solution is frozen suggesting that CH(3)OOH remains in a liquid layer between the ice grains. Using the extinction coefficients and photolysis quantum yields obtained in this work, we show that under conditions with low temperatures, in the presence of clouds with a high liquid-water content and large solar zenith angles, the loss of CH(3)OOH by aqueous photolysis is responsible for up to 20% of the total loss of CH(3)OOH due to photolysis. Gas phase photolysis of CH(3)OOH dominates under all other conditions.

  7. X-ray microprobe for micro x-ray fluorescence and absorption spectroscopies at GSECARS

    NASA Astrophysics Data System (ADS)

    Newville, M.; Sutton, S.; Rivers, M.

    2002-12-01

    The hard x-ray microprobe for x-ray fluorescence and absorption spectroscopy at GeoSoilEnviroCARS is presented. Using focused synchrotron radiation from an undulator beamline at the Advanced Photon Source at Argonne National Lab, the x-ray microprobe provides bright, monochromatic x-rays with typical spot sizes down to 1x1 μm for x-ray fluorescence and absorption spectroscopies. Quantitative x-ray fluorescence (XRF) analysis gives precise elemental composition and correlations, while x-ray absorption spectroscopy (XAS) gives the chemical state and local atomic coordination for a selected atomic species. These two techniques can be used in conjunction with one another on a wide range of samples, including minerals, glasses, fluid inclusions, soils, sediments, and plant tissue. This x-ray microprobe is part of the GeoSoilEnviroCARS user facility, available for use in all areas geological, soil, and environmental sciences, and selected examples from these fields will be given.

  8. Fluorescence upconversion properties of a class of improved pyridinium dyes induced by two-photon absorption

    NASA Astrophysics Data System (ADS)

    Xu, Guibao; Hu, Dawei; Zhao, Xian; Shao, Zongshu; Liu, Huijun; Tian, Yupeng

    2007-06-01

    We report the fluorescence upconversion properties of a class of improved pyridinium toluene- p-sulfonates having donor- π-acceptor (D- π-A) structure under two-photon excitation at 1064 nm. The experimental results show that both the two-photon excited (TPE) fluorescence lifetime and the two-photon pumped (TPP) energy upconversion efficiency were increased with the enhancement of electron-donating capability of the donor in the molecule. It is also indicated that an overlong alkyl group tends to result in a weakened molecular conjugation, leading to a decreased two-photon absorption (TPA) cross section. By choosing the donor, we can obtain a longest fluorescence lifetime of 837 ps, a highest energy upconversion efficiency of ˜6.1%, and a maximum TPA cross-section of 8.74×10 -48 cm 4 s/photon in these dyes.

  9. Computing the Absorption and Emission Spectra of 5-Methylcytidine in Different Solvents: A Test-Case for Different Solvation Models.

    PubMed

    Martínez-Fernández, L; Pepino, A J; Segarra-Martí, J; Banyasz, A; Garavelli, M; Improta, R

    2016-09-13

    The optical spectra of 5-methylcytidine in three different solvents (tetrahydrofuran, acetonitrile, and water) is measured, showing that both the absorption and the emission maximum in water are significantly blue-shifted (0.08 eV). The absorption spectra are simulated based on CAM-B3LYP/TD-DFT calculations but including solvent effects with three different approaches: (i) a hybrid implicit/explicit full quantum mechanical approach, (ii) a mixed QM/MM static approach, and (iii) a QM/MM method exploiting the structures issuing from molecular dynamics classical simulations. Ab-initio Molecular dynamics simulations based on CAM-B3LYP functionals have also been performed. The adopted approaches all reproduce the main features of the experimental spectra, giving insights on the chemical-physical effects responsible for the solvent shifts in the spectra of 5-methylcytidine and providing the basis for discussing advantages and limitations of the adopted solvation models. PMID:27529792

  10. A wavelength-dispersive instrument for characterizing fluorescence and scattering spectra of individual aerosol particles on a substrate

    NASA Astrophysics Data System (ADS)

    Huffman, Donald R.; Swanson, Benjamin E.; Huffman, J. Alex

    2016-08-01

    We describe a novel, low-cost instrument to acquire both elastic and inelastic (fluorescent) scattering spectra from individual supermicron-size particles in a multi-particle collection on a microscope slide. The principle of the device is based on a slitless spectroscope that is often employed in astronomy to determine the spectra of individual stars in a star cluster but had not been applied to atmospheric particles. Under excitation, most commonly by either a 405 nm diode laser or a UV light-emitting diode (LED), fluorescence emission spectra of many individual particles can be determined simultaneously. The instrument can also acquire elastic scattering spectra from particles illuminated by a white-light source. The technique also provides the ability to detect and rapidly estimate the number fraction of fluorescent particles that could contaminate a collection of non-fluorescent material, even without analyzing full spectra. Advantages and disadvantages of using black-and-white cameras compared to color cameras are given. The primary motivation for this work has been to develop an inexpensive technique to characterize fluorescent biological aerosol particles, especially particles such as pollen and mold spores that can cause allergies. An example of an iPhone-enabled device is also shown as a means for collecting data on biological aerosols at lower cost or by utilizing citizen scientists for expanded data collection.

  11. Optical Absorption Spectra and Excitons of Dye-Substrate Interfaces: Catechol on TiO2(110).

    PubMed

    Mowbray, Duncan John; Migani, Annapaola

    2016-06-14

    Optimizing the photovoltaic efficiency of dye-sensitized solar cells (DSSC) based on staggered gap heterojunctions requires a detailed understanding of sub-band gap transitions in the visible from the dye directly to the substrate's conduction band (CB) (type-II DSSCs). Here, we calculate the optical absorption spectra and spatial distribution of bright excitons in the visible region for a prototypical DSSC, catechol on rutile TiO2(110), as a function of coverage and deprotonation of the OH anchoring groups. This is accomplished by solving the Bethe-Salpeter equation (BSE) based on hybrid range-separated exchange and correlation functional (HSE06) density functional theory (DFT) calculations. Such a treatment is necessary to accurately describe the interfacial level alignment and the weakly bound charge transfer transitions that are the dominant absorption mechanism in type-II DSSCs. Our HSE06 BSE spectra agree semiquantitatively with spectra measured for catechol on anatase TiO2 nanoparticles. Our results suggest deprotonation of catechol's OH anchoring groups, while being nearly isoenergetic at high coverages, shifts the onset of the absorption spectra to lower energies, with a concomitant increase in photovoltaic efficiency. Further, the most relevant bright excitons in the visible region are rather intense charge transfer transitions with the electron and hole spatially separated in both the [110] and [001] directions. Such detailed information on the absorption spectra and excitons is only accessible via periodic models of the combined dye-substrate interface. PMID:27183273

  12. Probing symmetry and symmetry breaking in resonant soft-x-ray fluorescence spectra of molecules

    SciTech Connect

    Glans, P.; Gunnelin, K.; Guo, J.

    1997-04-01

    Conventional non-resonant soft X-ray emission brings about information about electronic structure through its symmetry and polarization selectivity, the character of which is governed by simple dipole rules. For centro-symmetric molecules with the emitting atom at the inversion center these rules lead to selective emission through the required parity change. For the more common classes of molecules which have lower symmetry or for systems with degenerate core orbitals (delocalized over identical sites), it is merely the local symmetry selectivity that provides a probe of the local atomic orbital contribution to the molecular orbital. For instance, in X-ray spectra of first row species the intensities essentially map the p-density at each particular atomic site, and, in a molecular orbital picture, the contribution of the local p-type atomic orbitals in the LCAO description of the molecular orbitals. The situation is different for resonant X-ray fluorescence spectra. Here strict parity and symmetry selectivity gives rise to a strong frequency dependence for all molecules with an element of symmetry. In addition to symmetry selectivity the strong frequency dependence of resonant X-ray emission is caused by the interplay between the shape of a narrow X-ray excitation energy function and the lifetime and vibrational broadenings of the resonantly excited core states. This interplay leads to various observable effects, such as linear dispersion, resonance narrowing and emission line (Stokes) doubling. Also from the point of view of polarization selectivity, the resonantly excited X-ray spectra are much more informative than the corresponding non-resonant spectra. Examples are presented for nitrogen, oxygen, and carbon dioxide molecules.

  13. [Study of the Detecting System of CH4 and SO2 Based on Spectral Absorption Method and UV Fluorescence Method].

    PubMed

    Wang, Shu-tao; Wang, Zhi-fang; Liu, Ming-hua; Wei, Meng; Chen, Dong-ying; Wang, Xing-long

    2016-01-01

    According to the spectral absorption characteristics of polluting gases and fluorescence characteristics, a time-division multiplexing detection system is designed. Through this system we can detect Methane (CH4) and sulfur dioxide (SO2) by using spectral absorption method and the SO2 can be detected by using UV fluorescence method. The system consists of four parts: a combination of a light source which could be switched, the common optical path, the air chamber and the signal processing section. The spectral absorption characteristics and fluorescence characteristics are measured first. Then the experiment of detecting CH4 and SO2 through spectral absorption method and the experiment of detecting SO2 through UV fluorescence method are conducted, respectively. Through measuring characteristics of spectral absorption and fluorescence, we get excitation wavelengths of SO2 and CH4 measured by spectral absorption method at the absorption peak are 280 nm and 1.64 μm, respectively, and the optimal excitation wavelength of SO2 measured by UV fluorescence method is 220 nm. we acquire the linear relation between the concentration of CH4 and relative intensity and the linear relation between the concentration of SO2 and output voltage after conducting the experiment of spectral absorption method, and the linearity are 98.7%, 99.2% respectively. Through the experiment of UV fluorescence method we acquire that the relation between the concentration of SO2 and the voltage is linear, and the linearity is 99.5%. Research shows that the system is able to be applied to detect the polluted gas by absorption spectrum method and UV fluorescence method. Combing these two measurement methods decreases the costing and the volume, and this system can also be used to measure the other gases. Such system has a certain value of application. PMID:27228784

  14. [Study of the Detecting System of CH4 and SO2 Based on Spectral Absorption Method and UV Fluorescence Method].

    PubMed

    Wang, Shu-tao; Wang, Zhi-fang; Liu, Ming-hua; Wei, Meng; Chen, Dong-ying; Wang, Xing-long

    2016-01-01

    According to the spectral absorption characteristics of polluting gases and fluorescence characteristics, a time-division multiplexing detection system is designed. Through this system we can detect Methane (CH4) and sulfur dioxide (SO2) by using spectral absorption method and the SO2 can be detected by using UV fluorescence method. The system consists of four parts: a combination of a light source which could be switched, the common optical path, the air chamber and the signal processing section. The spectral absorption characteristics and fluorescence characteristics are measured first. Then the experiment of detecting CH4 and SO2 through spectral absorption method and the experiment of detecting SO2 through UV fluorescence method are conducted, respectively. Through measuring characteristics of spectral absorption and fluorescence, we get excitation wavelengths of SO2 and CH4 measured by spectral absorption method at the absorption peak are 280 nm and 1.64 μm, respectively, and the optimal excitation wavelength of SO2 measured by UV fluorescence method is 220 nm. we acquire the linear relation between the concentration of CH4 and relative intensity and the linear relation between the concentration of SO2 and output voltage after conducting the experiment of spectral absorption method, and the linearity are 98.7%, 99.2% respectively. Through the experiment of UV fluorescence method we acquire that the relation between the concentration of SO2 and the voltage is linear, and the linearity is 99.5%. Research shows that the system is able to be applied to detect the polluted gas by absorption spectrum method and UV fluorescence method. Combing these two measurement methods decreases the costing and the volume, and this system can also be used to measure the other gases. Such system has a certain value of application.

  15. Correlating Fluorescence and Absorption Properties of Dissolved Organic Matter in Northern Peatland Soil Porewaters with Molecular Composition Information

    NASA Astrophysics Data System (ADS)

    Tfaily, M. M.; D'Andrilli, J.; Corbett, J.; Chanton, J.; Cooper, W. T.

    2009-12-01

    Northern peatlands store roughly half as much carbon as is stored as CO2 in the atmosphere in the form of complex biogeopolymers. As climate change proceeds, increasing carbon release from these historically carbon-sequestering environments may represent an unidentified forcing stress on global temperatures. In this work, we have applied absorption spectroscopy, Excitation/Emission Matrix (EEM) spectroscopy and ultrahigh resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS) to study the differences in composition of dissolved organic matter (DOM) in soil porewaters at varying depths from different sites (fens and bogs) within the Glacial Lake Agassiz Peatlands (GLAP) of northern Minnesota. UV/Vis absorbance and Excitation Emission Matrix Fluorescence Spectroscopy (EEMS) were used to identify changes in the optical properties associated with the chromophoric fractions of DOM (CDOM). Higher specific UV absorbance (SUVA) at 254 nm indicated relatively more aromatic content in the DOM in surface bog and deep fen horizons. EEMS results were also found to be in agreement with the absorption spectra and molecular characterization as determined by FT-ICR-MS. The strong correlations we have observed suggest that optical spectroscopy techniques represent an effective surrogate approach to characterizing the composition of DOM provided some detailed molecular information is available for calibrating the observed correlations.

  16. Molecular dynamics simulation and TDDFT study of the structures and UV-vis absorption spectra of MCT-β-CD and its inclusion complexes.

    PubMed

    Lu, Huijuan; Wang, Yujiao; Xie, Xiaomei; Chen, Feifei; Li, Wei

    2015-01-01

    In this research, the inclusion ratios and inclusion constants of MCT-β-CD/PERM and MCT-β-CD/CYPERM inclusion complexes were measured by UV-vis and fluorescence spectroscopy. The inclusion ratios are both 1:1, and the inclusion constants are 60 and 342.5 for MCT-β-CD/PERM and MCT-β-CD/CYPERM, respectively. The stabilities of inclusion complexes were investigated by MD simulation. MD shows that VDW energy plays a vital role in the stability of inclusion complex, and the destruction of inclusion complex is due to the increasing temperature. The UV-vis absorption spectra of MCT-β-CD and its inclusion complexes were studied by time-dependent density functional theory (TDDFT) method employing BLYP-D3, B3LYP-D3 and M06-2X-D3 functionals. BLYP-D3 well reproduces the UV-vis absorption spectrum and reveals that the absorption bands of MCT-β-CD mainly arise from n→π(∗) and n→σ(∗) transition, and those of inclusion complexes mainly arise from intramolecular charge transfer (ICT). ICT results in the shift of main absorption bands of MCT-β-CD.

  17. Effect of perfluorocarbons on the ultraviolet absorption and fluorescence characteristics of some saturated hydrocarbon liquids

    SciTech Connect

    Choi, H.T.; Lipsky, S.

    1981-12-24

    Perfluoro-n-alkanes and perfluorocycloalkanes are found to affect the photophysical properties of saturated hydrocarbons in markedly different ways.The addition of a low concentration (<0.2 M) of a perfluoro-n-alkane to a hydrocarbon liquid has no observable effect on the electronic absorption spectrum and only very slightly quenches the hydrocarbon fluorescence. In contrast, at the same concentration levels, the perfluorocycloalkane strongly perturbs the absorption spectrum and very effectively reduces the fluorescence quantum yield. The change in the absorption spectrum is attributed to a contact charge-transfer absorption with the hydrocarbon acting as electron donor. The efficiency with which the perfluorocycloalkane reduces the hydrocarbon fluorescence quantum yield increases with increasing perfluorocycloalkane concentration. The results are analyzed with a conventional diffusional model that includes transient terms. The model contains two parameters, an encounter distance, R, and the product of the relative diffusion coefficient, D, and the lifetime, tau/sub 0/, of the hydrocarbon excited state. The model is applied to perfluorodecalin quenching of cyclohexane, decalin, and 2,3-dimethylbutane at excitation wavelengths, lambda/sub ex/, ranging from 185 to 147 nm. An unrestricted, two-parameter, least-squares fit of the model to the data provides values of R and D(tau/sub 0/) for each solvent system at each lambda/sub ex/. Where values of D and tau/sub 0/ are known independently, their product agrees well with the D(tau/sub 0/) obtained from the fit. The value of R is found to be approx. = 14 angstrom for all solvents at all lambda/sub ex/. This value is estimated to be about 2 times larger than the ground-state hydrocarbon-perfluorodecalin contact distance.

  18. Soft X-ray absorption spectra of aqueous salt solutions with highly charged cations in liquid microjets

    SciTech Connect

    Schwartz, Craig P.; Uejio, Janel S.; Duffin, Andrew M.; Drisdell, Walter S.; Smith, Jared D.; Saykally, Richard J.

    2010-03-11

    X-ray absorption spectra of 1M aqueous solutions of indium (III) chloride, yttrium (III) bromide, lanthanum (III) chloride, tin (IV) chloride and chromium (III) chloride have been measured at the oxygen K-edge. Relatively minor changes are observed in the spectra compared to that of pure water. SnCl{sub 4} and CrCl{sub 3} exhibit a new onset feature which is attributed to formation of hydroxide or other complex molecules in the solution. At higher energy, only relatively minor, but salt-specific changes in the spectra occur. The small magnitude of the observed spectral changes is ascribed to offsetting perturbations by the cations and anions.

  19. Signatures in vibrational and UV-visible absorption spectra for identifying cyclic hydrocarbons by graphene fragments

    NASA Astrophysics Data System (ADS)

    Meng, Yan; Wu, Qi; Chen, Lei; Wangmo, Sonam; Gao, Yang; Wang, Zhigang; Zhang, Rui-Qin; Ding, Dajun; Niehaus, Thomas A.; Frauenheim, Thomas

    2013-11-01

    To promote possible applications of graphene in molecular identification based on stacking effects, in particular in recognizing aromatic amino acids and even sequencing nucleobases in life sciences, we comprehensively study the interaction between graphene segments and different cyclic organic hydrocarbons including benzene (C6H6), cyclohexane (C6H12), benzyne (C6H4), cyclohexene (C6H10), 1,3-cyclohexadiene (C6H8(1)) and 1,4-cyclohexadiene (C6H8(2)), using the density-functional tight-binding (DFTB) method. Interestingly, we find obviously different characteristics in Raman vibrational and ultraviolet visible absorption spectra of the small molecules adsorbed on the graphene sheet. Specifically, we find that both spectra involve clearly different characteristic peaks, belonging to the different small molecules upon adsorption, with the ones of ionized molecules being more substantial. Further analysis shows that the adsorptions are almost all due to the presence of dispersion energy in neutral cases and involve charge transfer from the graphene to the small molecules. In contrast, the main binding force in the ionic adsorption systems is the electronic interaction. The results present clear signatures that can be used to recognize different kinds of aromatic hydrocarbon rings on graphene sheets. We expect that our findings will be helpful for designing molecular recognition devices using graphene.To promote possible applications of graphene in molecular identification based on stacking effects, in particular in recognizing aromatic amino acids and even sequencing nucleobases in life sciences, we comprehensively study the interaction between graphene segments and different cyclic organic hydrocarbons including benzene (C6H6), cyclohexane (C6H12), benzyne (C6H4), cyclohexene (C6H10), 1,3-cyclohexadiene (C6H8(1)) and 1,4-cyclohexadiene (C6H8(2)), using the density-functional tight-binding (DFTB) method. Interestingly, we find obviously different characteristics in

  20. Detection of water vapour absorption around 363nm in measured atmospheric absorption spectra and its effect on DOAS evaluations

    NASA Astrophysics Data System (ADS)

    Lampel, Johannes; Polyansky, Oleg. L.; Kyuberis, Alexandra A.; Zobov, Nikolai F.; Tennyson, Jonathan; Lodi, Lorenzo; Pöhler, Denis; Frieß, Udo; Platt, Ulrich; Beirle, Steffen; Wagner, Thomas

    2016-04-01

    Water vapour is known to absorb light from the microwave region to the blue part of the visible spectrum at a decreasing magnitude. Ab-initio approaches to model individual absorption lines of the gaseous water molecule predict absorption lines until its dissociation limit at 243 nm. We present first evidence of water vapour absorption at 363 nm from field measurements based on the POKAZATEL absorption line list by Polyansky et al. (2016) using data from Multi-Axis differential optical absorption spectroscopy (MAX-DOAS) and Longpath (LP)-DOAS measurements. The predicted absorptions contribute significantly to the observed optical depths with up to 2 × 10‑3. Their magnitude correlates well (R2 = 0.89) to simultaneously measured well-established water vapour absorptions in the blue spectral range from 452-499 nm, but is underestimated by a factor of 2.6 ± 0.6 in the ab-initio model. At a spectral resolution of 0.5nm this leads to a maximum absorption cross-section value of 5.4 × 10‑27 cm2/molec at 362.3nm. The results are independent of the employed cross-section data to compensate for the overlayed absorption of the oxygen dimer O4. The newly found absorption can have a significant impact on the spectral retrieval of absorbing trace-gas species in the spectral range around 363 nm. Its effect on the spectral analysis of O4, HONO and OClO are discussed.

  1. High-Velocity Absorption Features in FUSE Spectra of Eta Carinae

    NASA Astrophysics Data System (ADS)

    Sonneborn, G.; Iping, R. C.; Gull, T. R.; Vieira, G.

    2002-12-01

    Numerous broad (200 to 1000 km/sec) features in the FUSE spectrum (905-1187 A) of eta Carinae are identified as absorption by a forest of high-velocity narrow lines formed in the expanding circumstellar envelope. These features were previously thought to be P-Cygni lines arising in the wind of the central star. The features span a heliocentric velocity range of -140 to -580 km/sec and are seen prominently in low-ionization ground-state transitions (e.g. N I 1134-35, Fe II 1145-42, 1133, 1127-22, P II 1153, C I 1158) in addition to C III] 1176 A. The high-velocity components of the FUSE transitions have depths about 50% below the continuum. The identifications are consistent with the complex velocity structures seen in ground- and excited-state transitions of Mg I, Mg II, Fe II, V II, etc observed in STIS/E230H spectra (see accompanying posters by Gull, Vieira, and Danks). The origin of other broad features of similar width and depth in the FUSE spectrum, but without low-velocity ISM absorption, are unidentified. However, they are suspected of being absorption of singly-ionized iron-peak elements (e.g. Fe II, V II, Cr II) out of excited levels 1,000 to 20,000 cmE-1 above the ground state. The high-velocity features seen in Fe II 1145 are also present in Fe II 1608 (STIS/E140M), but are highly saturated in the latter. Since these transitions have nearly identical log (flambda) (1.998 vs. 2.080), the differences in the profiles are attributable to the different aperture sizes used (30x30 arcsec for FUSE, 0.2x0.2 arcsec for STIS/E140M). The high-velocity gas appears to be very patchy or has a small covering factor near the central star. Eta Carinae has been observed several times by FUSE over the past three years. The FUSE flux levels and spectral features in eta Car are essentially unchanged over the 2000 March to June 2002 period, establishing a baseline far-UV spectrum in advance of the predicted spectroscopic miniumum in 2003.

  2. High-Velocity Absorption Features in FUSE Spectra of Eta Carinae

    NASA Technical Reports Server (NTRS)

    Sonneborn, G.; Iping, R. C.; Gull, T. R.; Vieira, G.

    2003-01-01

    Numerous broad (200 to 1000 km/sec) features in the FUSE spectrum (905-1187 A) of eta Carinae are identified as absorption by a forest of high-velocity narrow lines formed in the expanding circumstellar envelope. These features were previously thought to be P-Cygni lines arising in the wind of the central star. The features span a heliocentric velocity range of -140 to -580 km/sec and are seen prominently in low-ionization ground-state transitions (e.g. N I 1134-35, Fe II 1145-42, 1133, 1127- 22, P II 1153, C I 1158) in addition to C III] 1176 A. The high-velocity components of the FUSE transitions have depths about 50% below the continuum. The identifications are consistent with the complex velocity structures seen in ground- and excited-state transitions of Mg I, Mg 11, Fe II, V II, etc observed in STIS/E230H spectra. The origin of other broad features of similar width and depth in the FUSE spectrum, but without low-velocity ISM absorption, are unidentified. However, they are suspected of being absorption of singly-ionized iron-peak elements (e.g. Fe II, V II, Cr II) out of excited levels 1,000 to 20,000 cmE-l above the ground state. The high-velocity features seen in Fe II 1145 are also present in Fe II 1608 (STIS/E140M), but are highly saturated in the latter. Since these transitions have nearly identical log (flambda) (1.998 vs. 2.080), the differences in the profiles are attributable to the different aperture sizes used (30 x 30 arcsec for FUSE, 0.2 x 0.2 arcsec for STIS/E140M). The high-velocity gas appears to be very patchy or has a small covering factor near the central star. Eta Carinae has been observed several times by FUSE over the past three years. The FUSE flux levels and spectral features in eta Car are essentially unchanged over the 2000 March to June 2002 period, establishing a baseline far-UV spectrum in advance of the predicted spectroscopic minimum in 2003.

  3. Wavelet based de-noising of breath air absorption spectra profiles for improved classification by principal component analysis

    NASA Astrophysics Data System (ADS)

    Kistenev, Yu. V.; Shapovalov, A. V.; Borisov, A. V.; Vrazhnov, D. A.; Nikolaev, V. V.; Nikiforova, O. Yu.

    2015-11-01

    The comparison results of different mother wavelets used for de-noising of model and experimental data which were presented by profiles of absorption spectra of exhaled air are presented. The impact of wavelets de-noising on classification quality made by principal component analysis are also discussed.

  4. Optical Absorption Spectra of Cr3+ and Cr4+ in Sr3Ga2Ge4O14 Garnet Crystals

    NASA Astrophysics Data System (ADS)

    Xu, Jun; Deng, Peizhen; Zhang, Qiang; Gan, Fuxi

    1995-07-01

    Single crystals of Sr3Ga2Ge4O14:Cr are grown by the Czochralski method. The polarized optical absorption spectra of Cr in visible and near-infrared wavelength are presented and analyzed. It is suggested that Cr enters the octahedral and tetrahedral positions as Cr3+ and Cr4+ respectively.

  5. Influence of absorption and scattering on the quantification of fluorescence diffuse optical tomography using normalized data.

    PubMed

    Abascal, Juan Felipe Perez-Juste; Aguirre, Juan; Chamorro-Servent, Judit; Schweiger, Martin; Arridge, Simon; Ripoll, Jorge; Vaquero, Juan J; Desco, Manuel

    2012-03-01

    Reconstruction algorithms for imaging fluorescence in near infrared ranges usually normalize fluorescence light with respect to excitation light. Using this approach, we investigated the influence of absorption and scattering heterogeneities on quantification accuracy when assuming a homogeneous model and explored possible reconstruction improvements by using a heterogeneous model. To do so, we created several computer-simulated phantoms: a homogeneous slab phantom (P1), slab phantoms including a region with a two- to six-fold increase in scattering (P2) and in absorption (P3), and an atlas-based mouse phantom that modeled different liver and lung scattering (P4). For P1, reconstruction with the wrong optical properties yielded quantification errors that increased almost linearly with the scattering coefficient while they were mostly negligible regarding the absorption coefficient. This observation agreed with the theoretical results. Taking the quantification of a homogeneous phantom as a reference, relative quantification errors obtained when wrongly assuming homogeneous media were in the range +41 to +94% (P2), 0.1 to -7% (P3), and -39 to +44% (P4). Using a heterogeneous model, the overall error ranged from -7 to 7%. In conclusion, this work demonstrates that assuming homogeneous media leads to noticeable quantification errors that can be improved by adopting heterogeneous models.

  6. Influence of absorption and scattering on the quantification of fluorescence diffuse optical tomography using normalized data

    NASA Astrophysics Data System (ADS)

    Abascal, Juan Felipe Perez-Juste; Aguirre, Juan; Chamorro-Servent, Judit; Schweiger, Martin; Arridge, Simon; Ripoll, Jorge; Vaquero, Juan J.; Desco, Manuel

    2012-03-01

    Reconstruction algorithms for imaging fluorescence in near infrared ranges usually normalize fluorescence light with respect to excitation light. Using this approach, we investigated the influence of absorption and scattering heterogeneities on quantification accuracy when assuming a homogeneous model and explored possible reconstruction improvements by using a heterogeneous model. To do so, we created several computer-simulated phantoms: a homogeneous slab phantom (P1), slab phantoms including a region with a two- to six-fold increase in scattering (P2) and in absorption (P3), and an atlas-based mouse phantom that modeled different liver and lung scattering (P4). For P1, reconstruction with the wrong optical properties yielded quantification errors that increased almost linearly with the scattering coefficient while they were mostly negligible regarding the absorption coefficient. This observation agreed with the theoretical results. Taking the quantification of a homogeneous phantom as a reference, relative quantification errors obtained when wrongly assuming homogeneous media were in the range +41 to +94% (P2), 0.1 to -7% (P3), and -39 to +44% (P4). Using a heterogeneous model, the overall error ranged from -7 to 7%. In conclusion, this work demonstrates that assuming homogeneous media leads to noticeable quantification errors that can be improved by adopting heterogeneous models.

  7. Gravitationally redshifted absorption lines in the X-ray burst spectra of a neutron star.

    PubMed

    Cottam, J; Paerels, F; Mendez, M

    2002-11-01

    The fundamental properties of neutron stars provide a direct test of the equation of state of cold nuclear matter, a relationship between pressure and density that is determined by the physics of the strong interactions between the particles that constitute the star. The most straightforward method of determining these properties is by measuring the gravitational redshift of spectral lines produced in the neutron star photosphere. The equation of state implies a mass-radius relation, while a measurement of the gravitational redshift at the surface of a neutron star provides a direct constraint on the mass-to-radius ratio. Here we report the discovery of significant absorption lines in the spectra of 28 bursts of the low-mass X-ray binary EXO0748-676. We identify the most significant features with the Fe XXVI and XXV n = 2-3 and O VIII n = 1-2 transitions, all with a redshift of z = 0.35, identical within small uncertainties for the respective transitions. For an astrophysically plausible range of masses (M approximately 1.3-2.0 solar masses; refs 2-5), this value is completely consistent with models of neutron stars composed of normal nuclear matter, while it excludes some models in which the neutron stars are made of more exotic matter. PMID:12422210

  8. Temporal-frequency spectra for plane and spherical waves in a millimetric wave absorption band

    NASA Astrophysics Data System (ADS)

    Siqueira, Glaucio L.; Cole, Roy S.

    1991-02-01

    Complete analytical expressions for the temporal power spectral density functions in a millimetric wave absorption region for plane and spherical waves have been developed for both amplitude and phase fluctuations due to atmospheric turbulence. Asymptotic expressions for both high and low scintillation frequencies are derived. Theoretical expressions for the differential phase power spectrum (i.e., the phase difference between two frequencies) are also presented. Experimental results of amplitude and differential phase scintillations measured on a 4.1-km link across central London, are presented. Results show that the plane wave case gives the best agreement with theory for this particular link. It is also shown that neglecting the cross-spectral density term at the higher scintillation frequencies for the differential phase spectrum can lead to a large difference between the theoretical and experimental power spectra. In particular, for a small frequency separation and a large value of the outer scale of turbulence, the highest scintillation frequencies are too low to neglect the cross term.

  9. THz Absorption Spectra of Fe Water Complexes Interacting with O3 Calculated by Density Functional Theory

    NASA Astrophysics Data System (ADS)

    Huang, L.; Lambrakos, S. G.; Shabaev, A.; Massa, L.; Yapijakis, C.

    2013-05-01

    The need for better monitoring of water quality and levels of water contamination implies a need for determining the dielectric response properties of water contaminants with respect to electromagnetic wave excitation. In addition to monitoring contaminants, there is an associated need for monitoring chemical processes that are for deactivation or assistance in the removal of water contaminants. Iron and manganese are two naturally occurring water contaminants, where iron is in general at much higher concentrations. Correspondingly, a process that is highly effective for assisting filtration of water contaminants, including iron and manganese, is the addition in solution of Ozone, i.e., the preozonation process. The present study uses density functional theory (DFT) for the calculation of ground-state resonance structure associated with Fe water complexes interacting with Ozone in solution. The calculations presented are for excitation by electromagnetic waves at frequencies within the THz range. Dielectric response functions can provide for different types of analyses concerning water contaminants. In particular, dielectric response functions can provide quantitative initial estimates of spectral response features for subsequent adjustment with respect to additional information such as laboratory measurements and other types of theory-based calculations. In addition, with respect to qualitative analysis, DFT-calculated absorption spectra provide for molecular level interpretation of response structure. The DFT software GAUSSIAN was used for the calculations of ground-state resonance structure presented in this article.

  10. Absorption spectra and sunlight conversion efficiency in fullerene bonded supramolecules on nanostructured ZnO

    NASA Astrophysics Data System (ADS)

    Zakhidov, Erkin; Kokhkharov, Abdumutallib; Kuvondikov, Vakhobjon; Nematov, Sherzod; Nusretov, Rafael

    2015-10-01

    The efficiency of solar radiation conversion in a model system of artificial photosynthesis, the porphyrin-fullerene assembly, is analyzed. A study of the optical absorption spectra of the porphyrin and the fullerene molecules, as well as their assembly in organic solutions, made it possible to estimate the energy efficiency of the conversion. Numerical values of the energy efficiency, defined as the fraction of the light quantum energy converted to the chemical potential of separated charges, are calculated for low- and high-concentration solutions of such a supramolecular system. The possibility of the efficient utilization of long-wavelength solar radiation in the high-concentration porphyrin-fullerene assembly solution in toluene and benzene is shown. In the photovoltaic system consisting of such a supramolecular active element, a thin ZnO film with a nanostructured surface may be introduced as a secondary acceptor of electrons from fullerene molecules. An enhancement of the transformation of separated charges of the porphyrin-fullerene assembly into electrical current by means of the ZnO film deposited on the surface of the anode electrode in such a heterogenic photovoltaic unit is proposed.

  11. Identifying student and teacher difficulties in interpreting atomic spectra using a quantum model of emission and absorption of radiation

    NASA Astrophysics Data System (ADS)

    Savall-Alemany, Francisco; Domènech-Blanco, Josep Lluís; Guisasola, Jenaro; Martínez-Torregrosa, Joaquín

    2016-06-01

    Our study sets out to identify the difficulties that high school students, teachers, and university students encounter when trying to explain atomic spectra. To do so, we identify the key concepts that any quantum model for the emission and absorption of electromagnetic radiation must include to account for the gas spectra and we then design two questionnaires, one for teachers and the other for students. By analyzing the responses, we conclude that (i) teachers lack a quantum model for the emission and absorption of electromagnetic radiation capable of explaining the spectra, (ii) teachers and students share the same difficulties, and (iii) these difficulties concern the model of the atom, the model of radiation, and the model of the interaction between them.

  12. Ultrafast absorption difference spectra of the Fenna-Matthews-Olson protein at 19 K: experiment and simulations.

    PubMed Central

    Buck, D R; Savikhin, S; Struve, W S

    1997-01-01

    We describe simulations of absorption difference spectra in strongly coupled photosynthetic antennas. In the presence of large resonance couplings, distinctive features arise from excited-state absorption transitions between one- and two-exciton levels. We first outline the theory for the heterodimer and for the general N-pigment system, and we demonstrate the transition between the strong and weak coupling regimes. The theory is applied to Fenna-Matthews-Olson (FMO) bacteriochlorophyll a protein trimers from the green photosynthetic bacterium Prosthecochloris aestuarii and then compared with experimental low-temperature absorption difference spectra of FMO trimers from the green bacterium Chlorobium tepidum. Images FIGURE 1 FIGURE 7 FIGURE 8 FIGURE 12 PMID:8994590

  13. Transient absorption spectroscopy detection of sensitized delayed fluorescence in chiral benzophenone/naphthalene systems

    NASA Astrophysics Data System (ADS)

    Bonancía, Paula; Jiménez, M. Consuelo; Miranda, Miguel A.

    2011-10-01

    Transient absorption spectroscopy has proven to be a powerful tool to investigate the formation and decay of excited singlet states upon triplet-triplet annihilation, following T-T energy transfer from a selectively excited sensitizer. Thus, upon selective excitation of benzophenone (BZP) by laser flash photolysis (LFP) at λ = 355 nm in the presence of naphthalene (NPT), a negative band centered at 340 nm has been detected, with growth and decay in the microsecond timescale. It has been assigned to the P-type NPT delayed-fluorescence. In the case of chiral BZP/NPT systems, stereodifferentiation has been observed in the kinetics of the involved photophysical processes.

  14. Investigation of two-photon absorption properties in new A-D-A compounds emitting blue and yellow fluorescence

    NASA Astrophysics Data System (ADS)

    Jin, Fan; Cai, Zhi-Bin; Huang, Jiu-Qiang; Li, Sheng-Li; Tian, Yu-Peng

    2015-08-01

    Three new acceptor-donor-acceptor compounds (LBQ, DBQ, BYQ) were synthesized and characterized by infrared, hydrogen nuclear magnetic resonance, mass spectrometry and elemental analysis. Their photophysical properties were investigated including linear absorption, single-photon excited fluorescence, fluorescence quantum yield and two-photon absorption. These compounds in CH2Cl2 exhibit good fluorescence quantum yield which are 0.36, 0.26, and 0.25 and the largest two-photon absorption cross-section which are 48, 36, and 181 GM respectively. Under the excitation of Ti: sapphire laser with a pulse width of 140 fs, LBQ and DBQ emit blue two-photon excited fluorescence (TPEF), while BYQ emits bright yellow TPEF. BYQ has a good solubility in water and the σ can be as large as 130 GM, so it shows promising applications in many pharmaceutical and biological fields.

  15. Quantitative analysis of deconvolved X-ray absorption near-edge structure spectra: a tool to push the limits of the X-ray absorption spectroscopy technique.

    PubMed

    D'Angelo, Paola; Migliorati, Valentina; Persson, Ingmar; Mancini, Giordano; Della Longa, Stefano

    2014-09-15

    A deconvolution procedure has been applied to K-edge X-ray absorption near-edge structure (XANES) spectra of lanthanoid-containing solid systems, namely, hexakis(dmpu)praseodymium(III) and -gadolinium(III) iodide. The K-edges of lanthanoids cover the energy range 38 (La)-65 (Lu) keV, and the large widths of the core-hole states lead to broadening of spectral features, reducing the content of structural information that can be extracted from the raw X-ray absorption spectra. Here, we demonstrate that deconvolution procedures allow one to remove most of the instrumental and core-hole lifetime broadening in the K-edge XANES spectra of lanthanoid compounds, highlighting structural features that are lost in the raw data. We show that quantitative analysis of the deconvolved K-edge XANES spectra can be profitably used to gain a complete local structural characterization of lanthanoid-containing systems not only for the nearest neighbor atoms but also for higher-distance coordination shells. PMID:25171598

  16. Analysis of Gain and Absorption Spectra of Gallium Nitride-based Laser Diodes

    NASA Astrophysics Data System (ADS)

    Melo, Thiago

    Laser diodes (LDs) based on the III-Nitride material system, (Al,In,Ga)N, stand to satisfy a number of application needs, and their huge market segment has been further growing with the use of LDs for full color laser projection. All commercially available GaN-based devices are based on the conventional c-plane (polar) orientation of this material. However, strong polarization fields caused by strained quantum-well (QW) layers on c-plane induce the quantum-confined Stark effect (QCSE), which leads to reduced radiative recombination rate and are aggravated when more indium is added into the QW(s) in order to achieve longer wavelengths. A promising solution for this is the use of nonpolar and semipolar crystal growth orientations. Elimination or mitigation of polarization-related fields within the QWs grown along these novel orientations is observed and one expects increased radiative recombination rate and stabilization of the wavelength emission with respect to the injection current. In order to have more insights on the advantages of using the novel crystal orientations of the III-Nitride material system, we compare the gain of LD structures fabricated from c-plane, nonpolar and semipolar GaN substrates. Using thesegmented contact method, single-pass gain spectra of LD epitaxial structures at wafer level are compared for the different crystal orientations as well as the single-pass absorption coefficient spectrum of the active region material and its dependence on reversed bias. Experimental gain spectra under continuous-wave (CW) operation of actual industry LDs fabricated from c-plane and nonpolar/semipolar GaN-based materials emitting wavelengths in the visible are then presented, using the Hakki-Paoli technique at high resolution. Measurements of the transparency current density, total losses and differential modal gain curves up to threshold are analyzed and compared between nonpolar/semipolar and c-plane LDs in violet and blue spectral regions regions. In a

  17. Comparison of x-ray absorption spectra between water and ice: new ice data with low pre-edge absorption cross-section.

    PubMed

    Sellberg, Jonas A; Kaya, Sarp; Segtnan, Vegard H; Chen, Chen; Tyliszczak, Tolek; Ogasawara, Hirohito; Nordlund, Dennis; Pettersson, Lars G M; Nilsson, Anders

    2014-07-21

    The effect of crystal growth conditions on the O K-edge x-ray absorption spectra of ice is investigated through detailed analysis of the spectral features. The amount of ice defects is found to be minimized on hydrophobic surfaces, such as BaF2(111), with low concentration of nucleation centers. This is manifested through a reduction of the absorption cross-section at 535 eV, which is associated with distorted hydrogen bonds. Furthermore, a connection is made between the observed increase in spectral intensity between 544 and 548 eV and high-symmetry points in the electronic band structure, suggesting a more extended hydrogen-bond network as compared to ices prepared differently. The spectral differences for various ice preparations are compared to the temperature dependence of spectra of liquid water upon supercooling. A double-peak feature in the absorption cross-section between 540 and 543 eV is identified as a characteristic of the crystalline phase. The connection to the interpretation of the liquid phase O K-edge x-ray absorption spectrum is extensively discussed.

  18. Comparison of x-ray absorption spectra between water and ice: New ice data with low pre-edge absorption cross-section

    SciTech Connect

    Sellberg, Jonas A.; Nilsson, Anders; Kaya, Sarp; Segtnan, Vegard H.; Chen, Chen; Tyliszczak, Tolek; Ogasawara, Hirohito; Nordlund, Dennis; Pettersson, Lars G. M.

    2014-07-21

    The effect of crystal growth conditions on the O K-edge x-ray absorption spectra of ice is investigated through detailed analysis of the spectral features. The amount of ice defects is found to be minimized on hydrophobic surfaces, such as BaF{sub 2}(111), with low concentration of nucleation centers. This is manifested through a reduction of the absorption cross-section at 535 eV, which is associated with distorted hydrogen bonds. Furthermore, a connection is made between the observed increase in spectral intensity between 544 and 548 eV and high-symmetry points in the electronic band structure, suggesting a more extended hydrogen-bond network as compared to ices prepared differently. The spectral differences for various ice preparations are compared to the temperature dependence of spectra of liquid water upon supercooling. A double-peak feature in the absorption cross-section between 540 and 543 eV is identified as a characteristic of the crystalline phase. The connection to the interpretation of the liquid phase O K-edge x-ray absorption spectrum is extensively discussed.

  19. Bespoke contrast-matched diblock copolymer nanoparticles enable the rational design of highly transparent Pickering double emulsions† †Electronic supplementary information (ESI) available: GPC chromatograms, additional transmission electron micrographs, digital photographs, visible absorption spectra and laser diffraction data, further optical and fluorescence micrographs. See DOI: 10.1039/c6nr03856e Click here for additional data file.

    PubMed Central

    Thompson, Kate L.; Derry, Matthew J.; Warren, Nicholas J.; Ratcliffe, Liam P. D.; Williams, Clive N.; Brown, Steven L.

    2016-01-01

    We report the preparation of highly transparent oil-in-water Pickering emulsions using contrast-matched organic nanoparticles. This is achieved via addition of judicious amounts of either sucrose or glycerol to an aqueous dispersion of poly(glycerol monomethacrylate)56–poly(2,2,2-trifluoroethyl methacrylate)500 [PGMA–PTFEMA] diblock copolymer nanoparticles prior to high shear homogenization with an equal volume of n-dodecane. The resulting Pickering emulsions comprise polydisperse n-dodecane droplets of 20–100 μm diameter and exhibit up to 96% transmittance across the visible spectrum. In contrast, control experiments using non-contrast-matched poly(glycerol monomethacrylate)56–poly(benzyl methacrylate)300 [PGMA56–PBzMA300] diblock copolymer nanoparticles as a Pickering emulsifier only produced conventional highly turbid emulsions. Thus contrast-matching of the two immiscible phases is a necessary but not sufficient condition for the preparation of highly transparent Pickering emulsions: it is essential to use isorefractive nanoparticles in order to minimize light scattering. Furthermore, highly transparent oil-in-water-in-oil Pickering double emulsions can be obtained by homogenizing the contrast-matched oil-in-water Pickering emulsion prepared using the PGMA56–PTFEMA500 nanoparticles with a contrast-matched dispersion of hydrophobic poly(lauryl methacrylate)39–poly(2,2,2-trifluoroethyl methacrylate)800 [PLMA39–PTFEMA800] diblock copolymer nanoparticles in n-dodecane. Finally, we show that an isorefractive oil-in-water Pickering emulsion enables fluorescence spectroscopy to be used to monitor the transport of water-insoluble small molecules (pyrene and benzophenone) between n-dodecane droplets. Such transport is significantly less efficient than that observed for the equivalent isorefractive surfactant-stabilized emulsion. Conventional turbid emulsions do not enable such a comparison to be made because the intense light scattering leads to

  20. On-the-Fly ab Initio Semiclassical Dynamics of Floppy Molecules: Absorption and Photoelectron Spectra of Ammonia.

    PubMed

    Wehrle, Marius; Oberli, Solène; Vaníček, Jiří

    2015-06-01

    We investigate the performance of on-the-fly ab initio (OTF-AI) semiclassical dynamics combined with the thawed Gaussian approximation (TGA) for computing vibrationally resolved absorption and photoelectron spectra. Ammonia is used as a prototype of floppy molecules, whose potential energy surfaces display strong anharmonicity. We show that despite complications due to the presence of large amplitude motion, the main features of the spectra are captured by the OTF-AI-TGA, which—by definition—does not require any a priori knowledge of the potential energy surface. Moreover, the computed spectra are significantly better than those based on the popular global harmonic approximation. Finally, we probe the limit of the TGA to describe higher-resolution spectra, where long time dynamics is required. PMID:25928833

  1. Collison-induced rototranslational absorption spectra of H/sub 2/-He pairs at temperatures from 40 to 3000 K

    SciTech Connect

    Borysow, J.; Frommhold, L.; Birnbaum, G.

    1988-03-01

    The zeroth, first, and second spectral moments of the rototranslational collision-induced absorption (RT CIA) spectra of hydrogen-helium mixtures are calculated from the fundamental theory, for temperatures from 40 to 3000 K. With the help of simple analytical functions of three parameters and the information given, the RT CIA spectra of H/sub 2/-He pairs can be generated on computers of small capacity, with rms deviations from exact quantum profiles of not more than a few percent. Such representations of the CIA spectra are of interest for work related to the atmospheres of the outer planets and cool stars. The theoretical spectra are in close agreement with existing laboratory measurements at various temperatures from about 77 to 3000 K. 28 references.

  2. Collison-induced rototranslational absorption spectra of H2-He pairs at temperatures from 40 to 3000 K

    NASA Technical Reports Server (NTRS)

    Borysow, Jacek; Frommhold, Lothar; Birnbaum, George

    1988-01-01

    The zeroth, first, and second spectral moments of the rototranslational collision-induced absorption (RT CIA) spectra of hydrogen-helium mixtures are calculated from the fundamental theory, for temperatures from 40 to 3000 K. With the help of simple analytical functions of three parameters and the information given, the RT CIA spectra of H2-He pairs can be generated on computers of small capacity, with rms deviations from exact quantum profiles of not more than a few percent. Such representations of the CIA spectra are of interest for work related to the atmospheres of the outer planets and cool stars. The theoretical spectra are in close agreement with existing laboratory measurements at various temperatures from about 77 to 3000 K.

  3. A New Method for the Determination of Potassium Sorbate Combining Fluorescence Spectra Method with PSO-BP Neural Network.

    PubMed

    Wang, Shu-tao; Chen, Dong-ying; Wang, Xing-long; Wei, Meng; Wang, Zhi-fang

    2015-12-01

    In this paper, fluorescence spectra properties of potassium sorbate in aqueous solution and orange juice are studied, and the result.shows that in two solution there are many difference in fluorescence spectra of potassium sorbate, but the fluorescence characteristic peak exists in λ(ex)/λ(em) = 375/490 nm. It can be seen from the two dimensional fluorescence spectra that the relationship between the fluorescence intensity and the concentration of potassium sorbate is very complex, so there is no linear relationship between them. To determine the concentration of potassium sorbate in orange juice, a new method combining Particle Swarm Optimization (PSO) algorithm with Back Propagation (BP) neural network is proposed. The relative error of two predicted concentrations is 1.83% and 1.53% respectively, which indicate that the method is feasible. The PSO-BP neural network can accurately measure the concentration of potassium sorbate in orange juice in the range of 0.1-2.0 g · L⁻¹. PMID:26964248

  4. Electronic absorption spectra of rare earth (III) species in NaCl-2CsCl eutectic based melts

    NASA Astrophysics Data System (ADS)

    Volkovich, V. A.; Ivanov, A. B.; Yakimov, S. M.; Tsarevskii, D. V.; Golovanova, O. A.; Sukhikh, V. V.; Griffiths, T. R.

    2016-09-01

    Electronic absorption spectra of ions of trivalent rare earth elements were measured in the melts based on NaCl-2CsCl eutectic in the wavelength ranges of 190-1350 and 1450-1700 nm. The measurements were performed at 550-850 °C. The EAS of Y, La, Ce and Lu containing melts have no absorption bands in the studied regions. For the remaining REEs (Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb) the absorption bands in the EAS were assigned to the corresponding f-f electron transitions. The Stark effect was observed for Yb(III) F5/2 excited state. Increasing temperature leads to decreasing intensity of the absorption bands, except for the bands resulting from hypersensitive transitions. Beer's law was confirmed up to 0.4 M solutions of REE.

  5. Excitations, optical absorption spectra, and optical excitonic gaps of heterofullerenes. I. C60, C59N+, and C48N12: theory and experiment.

    PubMed

    Xie, Rui-Hua; Bryant, Garnett W; Sun, Guangyu; Nicklaus, Marc C; Heringer, David; Frauenheim, Th; Manaa, M Riad; Smith, Vedene H; Araki, Yasuyuki; Ito, Osamu

    2004-03-15

    Low-energy excitations and optical absorption spectrum of C(60) are computed by using time-dependent (TD) Hartree-Fock, TD-density functional theory (TD-DFT), TD DFT-based tight-binding (TD-DFT-TB), and a semiempirical Zerner intermediate neglect of diatomic differential overlap method. A detailed comparison of experiment and theory for the excitation energies, optical gap, and absorption spectrum of C(60) is presented. It is found that electron correlations and correlation of excitations play important roles in accurately assigning the spectral features of C(60), and that the TD-DFT method with nonhybrid functionals or a local spin density approximation leads to more accurate excitation energies than with hybrid functionals. The level of agreement between theory and experiment for C(60) justifies similar calculations of the excitations and optical absorption spectrum of a monomeric azafullerene cation C(59)N(+), to serve as a spectroscopy reference for the characterization of carborane anion salts. Although it is an isoelectronic analogue to C(60), C(59)N(+) exhibits distinguishing spectral features different from C(60): (1) the first singlet is dipole-allowed and the optical gap is redshifted by 1.44 eV; (2) several weaker absorption maxima occur in the visible region; (3) the transient triplet-triplet absorption at 1.60 eV (775 nm) is much broader and the decay of the triplet state is much faster. The calculated spectra of C(59)N(+) characterize and explain well the measured ultraviolet-visible (UV-vis) and transient absorption spectra of the carborane anion salt [C(59)N][Ag(CB(11)H(6)Cl(6))(2)] [Kim et al., J. Am. Chem. Soc. 125, 4024 (2003)]. For the most stable isomer of C(48)N(12), we predict that the first singlet is dipole-allowed, the optical gap is redshifted by 1.22 eV relative to that of C(60), and optical absorption maxima occur at 585, 528, 443, 363, 340, 314, and 303 nm. We point out that the characterization of the UV-vis and transient absorption

  6. Excitations, optical absorption spectra, and optical excitonic gaps of heterofullerenes. I. C60, C59N+, and C48N12: Theory and experiment

    NASA Astrophysics Data System (ADS)

    Xie, Rui-Hua; Bryant, Garnett W.; Sun, Guangyu; Nicklaus, Marc C.; Heringer, David; Frauenheim, Th.; Manaa, M. Riad; Smith, Vedene H.; Araki, Yasuyuki; Ito, Osamu

    2004-03-01

    Low-energy excitations and optical absorption spectrum of C60 are computed by using time-dependent (TD) Hartree-Fock, TD-density functional theory (TD-DFT), TD DFT-based tight-binding (TD-DFT-TB), and a semiempirical Zerner intermediate neglect of diatomic differential overlap method. A detailed comparison of experiment and theory for the excitation energies, optical gap, and absorption spectrum of C60 is presented. It is found that electron correlations and correlation of excitations play important roles in accurately assigning the spectral features of C60, and that the TD-DFT method with nonhybrid functionals or a local spin density approximation leads to more accurate excitation energies than with hybrid functionals. The level of agreement between theory and experiment for C60 justifies similar calculations of the excitations and optical absorption spectrum of a monomeric azafullerene cation C59N+, to serve as a spectroscopy reference for the characterization of carborane anion salts. Although it is an isoelectronic analogue to C60, C59N+ exhibits distinguishing spectral features different from C60: (1) the first singlet is dipole-allowed and the optical gap is redshifted by 1.44 eV; (2) several weaker absorption maxima occur in the visible region; (3) the transient triplet-triplet absorption at 1.60 eV (775 nm) is much broader and the decay of the triplet state is much faster. The calculated spectra of C59N+ characterize and explain well the measured ultraviolet-visible (UV-vis) and transient absorption spectra of the carborane anion salt [C59N][Ag(CB11H6Cl6)2] [Kim et al., J. Am. Chem. Soc. 125, 4024 (2003)]. For the most stable isomer of C48N12, we predict that the first singlet is dipole-allowed, the optical gap is redshifted by 1.22 eV relative to that of C60, and optical absorption maxima occur at 585, 528, 443, 363, 340, 314, and 303 nm. We point out that the characterization of the UV-vis and transient absorption spectra of C48N12 isomers is helpful in

  7. Interpretation of X-ray absorption spectra of As(III) in solution using Monte Carlo simulations.

    PubMed

    Canche-Tello, Jesus; Vargas, M Cristina; Hérnandez-Cobos, Jorge; Ortega-Blake, Iván; Leclercq, Amelie; Solari, Pierre Lorenzo; Den Auwer, Christophe; Mustre de Leon, José

    2014-11-20

    We performed X-ray absorption spectroscopy measurements on the arsenic K-edge of As(III) in solution under acidic conditions. Extended X-ray absorption fine structure (EXAFS) and X-ray near edge structure (XANES) spectra were compared with theoretical calculations which use local atomic structure configurations, either derived from density functional theory (DFT) energy minimization (EM) calculations or based on classical Monte Carlo (MC) simulations, for a As(OH)3 cluster surrounded by water molecules. The nearest arsenic-oxygen distances obtained from the fit of the XAFS spectra are consistent with the distances present in configurations derived from Monte Carlo simulations but not with those obtained from DFT-EM calculations. Calculations of XANES using either DFT-EM or the average configuration obtained from MC simulations do not reproduce the XANES spectra in the vicinity of the absorption edge. However, specific local atomic structural configurations of the As(OH)3 and water molecules, obtained from MC simulations, which show some ordering of water molecules up to 5 Å from the arsenic, reproduce qualitatively the experimental spectra. These results highlight the capability of XANES to yield information about hydration of ions in solution.

  8. Electronic Absorption Spectra of Tetrapyrrole-Based Pigments via TD-DFT: A Reduced Orbital Space Study.

    PubMed

    Shrestha, Kushal; Virgil, Kyle A; Jakubikova, Elena

    2016-07-28

    Tetrapyrrole-based pigments play a crucial role in photosynthesis as principal light absorbers in light-harvesting chemical systems. As such, accurate theoretical descriptions of the electronic absorption spectra of these pigments will aid in the proper description and understanding of the overall photophysics of photosynthesis. In this work, time-dependent density functional theory (TD-DFT) at the CAM-B3LYP/6-31G* level of theory is employed to produce the theoretical absorption spectra of several tetrapyrrole-based pigments. However, the application of TD-DFT to large systems with several hundreds of atoms can become computationally prohibitive. Therefore, in this study, TD-DFT calculations with reduced orbital spaces (ROSs) that exclude portions of occupied and virtual orbitals are pursued as a viable, computationally cost-effective alternative to conventional TD-DFT calculations. The effects of reducing orbital space size on theoretical spectra are qualitatively and quantitatively described, and both conventional and ROS results are benchmarked against experimental absorption spectra of various tetrapyrrole-based pigments. The orbital reduction approach is also applied to a large natural pigment assembly that comprises the principal light-absorbing component of the reaction center in purple bacteria. Overall, we find that TD-DFT calculations with proper and judicious orbital space reductions can adequately reproduce conventional, full orbital space, TD-DFT results of all pigments studied in this work.

  9. Study of electron transition energies between anions and cations in spinel ferrites using differential UV-vis absorption spectra

    NASA Astrophysics Data System (ADS)

    Xue, L. C.; Wu, L. Q.; Li, S. Q.; Li, Z. Z.; Tang, G. D.; Qi, W. H.; Ge, X. S.; Ding, L. L.

    2016-07-01

    It is very important to determine electron transition energies (Etr) between anions and different cations in order to understand the electrical transport and magnetic properties of a material. Many authors have analyzed UV-vis absorption spectra using the curve (αhν)2 vs E, where α is the absorption coefficient and E(=hν) is the photon energy. Such an approach can give only two band gap energies for spinel ferrites. In this paper, using differential UV-vis absorption spectra, dα/dE vs E, we have obtained electron transition energies (Etr) between the anions and cations, Fe2+ and Fe3+ at the (A) and [B] sites and Ni2+ at the [B] sites for the (A)[B]2O4 spinel ferrite samples CoxNi0.7-xFe2.3O4 (0.0≤x≤0.3), CrxNi0.7Fe2.3-xO4 (0.0≤x≤0.3) and Fe3O4. We suggest that the differential UV-vis absorption spectra should be accepted as a general analysis method for determining electron transition energies between anions and cations.

  10. Recording of absorption spectra by a three-beam integral technique with a tunable laser and external cavity

    SciTech Connect

    Korolenko, P V; Nikolaev, I V; Ochkin, V N; Tskhai, S N

    2014-04-28

    An integral method is considered for recording absorption using three laser beams transmitted through and reflected from an external cavity with the absorbing medium (R-ICOS). The method is the elaboration of a known single-beam ICOS method and allows suppression of the influence of radiation phase fluctuations in the resonator on recording weak absorption spectra. First of all, this reduces high-frequency instabilities and gives a possibility to record spectra during short time intervals. In this method, mirrors of the resonator may have moderate reflection coefficients. Capabilities of the method have been demonstrated by the examples of weak absorption spectra of atmospheric methane and natural gas in a spectral range around 1650 nm. With the mirrors having the reflection coefficients of 0.8–0.99, a spectrum can be recorded for 320 μs with the accuracy sufficient for detecting a background concentration of methane in atmosphere. For the acquisition time of 20 s, the absorption coefficients of ∼2×10{sup -8} cm{sup -1} can be measured, which corresponds to a 40 times less molecule concentration than the background value. (laser spectroscopy)

  11. Interpretation of unexpected behavior of infrared absorption spectra of ScF3 beyond the quasiharmonic approximation

    NASA Astrophysics Data System (ADS)

    Piskunov, Sergei; Žguns, Pjotrs A.; Bocharov, Dmitry; Kuzmin, Alexei; Purans, Juris; Kalinko, Aleksandr; Evarestov, Robert A.; Ali, Shehab E.; Rocca, Francesco

    2016-06-01

    Scandium fluoride (ScF3), having cubic ReO3-type structure, has attracted much scientific attention due to its rather strong negative thermal expansion (NTE) in the broad temperature range from 10 to 1100 K. Here we use the results of diffraction and extended x-ray absorption fine-structure (EXAFS) spectroscopy to interpret the influence of NTE on the temperature dependence of infrared absorption spectra of ScF3. Original infrared absorption and EXAFS experiments in a large temperature range are presented and interpreted using ab initio lattice dynamics simulations within and beyond quasiharmonic approximations. We demonstrate that ab initio electronic structure calculations, based on the linear combination of atomic orbitals method with hybrid functionals, are able to reproduce well the experimental values of lattice parameter a0, band gap Eg, and lattice dynamics in ScF3. However, the simulations performed within quasiharmonic approximation fail to reproduce the temperature dependence of two infrared active bands due to the F-Sc-F bending (at 220 cm-1) and Sc-F stretching (at 520 cm-1) modes present in the infrared absorption spectra. To overcome this problem, an approach beyond the quasiharmonic approximation is proposed: It accounts for the negative thermal expansion of the lattice and for fluorine atom displacements due to strong F vibrational motion perpendicular to the cubic axes and allows us to explain qualitatively the temperature behavior of infrared spectra of ScF3.

  12. Investigation on the spectral properties of 2D asynchronous fluorescence spectra generated by using variable excitation wavelengths as a perturbation

    NASA Astrophysics Data System (ADS)

    Wang, Jingdan; He, Anqi; Guo, Ran; Wei, Yongju; Feng, Juan; Xu, Yizhuang; Noda, Isao; Wu, Jinguang

    2016-11-01

    Properties of 2D asynchronous spectra generated from a series of fluorescence emission spectra are investigated. Variable excitation wavelengths are utilized as an external perturbation. Based on the results of mathematical analysis and computer simulation, we find that no cross peak will be produced on the 2D asynchronous spectrum if the fluorescent solute under investigation occurs in a single micro-environment. The observation of cross peaks implies that the fluorescent molecule may occur in different micro-environments in a solution. Based on these results, we use 2D asynchronous spectra to investigate the emission spectra of anthracene dissolved in cyclohexane. When the concentration of anthracene is low, no cross peak is produced in the resultant 2D asynchronous spectrum, confirming that anthracene is dissolved as single molecule in the solution. As the concentration elevated, cross peaks appear in the corresponding 2D asynchronous spectra. A plausible explanation of this phenomenon is that anthracene may undergo aggregation via π-π interaction or π-C-H interaction.

  13. Variability, absorption features, and parent body searches in "spectrally featureless" meteorite reflectance spectra: Case study - Tagish Lake

    NASA Astrophysics Data System (ADS)

    Izawa, M. R. M.; Craig, M. A.; Applin, D. M.; Sanchez, J. A.; Reddy, V.; Le Corre, L.; Mann, P.; Cloutis, E. A.

    2015-07-01

    Reflectance spectra of many asteroids and other Solar System bodies are commonly reported as "featureless". Here, we show that weak but consistently detectable absorption bands are observable in 200-2500 nm spectra of the Tagish Lake meteorite, a likely compositional and spectral analogue for low-albedo, "spectrally-featureless" asteroids. Tagish Lake presents a rare opportunity to study multiple lithologies within a single meteorite. Reflectance spectra of Tagish Lake display significant variation between different lithologies. The spectral variations are due in part to mineralogical variations between different Tagish Lake lithologies. Ultraviolet reflectance spectra (200-400 nm), few of which have been reported in the literature to date, reveal albedo and spectral ratio variations as a function of mineralogy. Similarly visible-near infrared reflectance spectra reveal variations in albedo, spectral slope, and the presence of weak absorption features that persist across different lithologies and can be attributed to various phases present in Tagish Lake. These observations demonstrate that significant spectral variability may exist between different lithologies of Tagish Lake, which may affect the interpretation of potential source body spectra. It is also important to consider the spectral variability within the meteorite before excluding compositional links between possible parent bodies in the main belt and Tagish Lake. Tagish Lake materials may also be spectral-compositional analogues for materials on the surfaces of other dark asteroids, including some that are targets of upcoming spacecraft missions. Tagish Lake has been proposed as a spectral match for 'ultra-primitive' D or P-type asteroids, and the variability reported here may be reflected in spatially or rotationally-resolved spectra of possible Tagish Lake parent bodies and source objects in the Near-Earth Asteroid population. A search for objects with spectra similar to Tagish Lake has been carried

  14. Real-time detection and characterization of individual flowing airborne biological particles: fluorescence spectra and elastic scattering measurements

    NASA Astrophysics Data System (ADS)

    Pan, Yongle; Holler, Stephen; Chang, Richard K.; Hill, Steven C.; Pinnick, Ronald G.; Niles, Stanley; Bottiger, Jerold R.; Bronk, Burt V.

    1999-11-01

    Real-time methods which is reagentless and could detect and partially characterize bioaerosols are of current interest. We present a technique for real-time measurement of UV-excited fluorescence spectra and two-dimensional angular optical scattering (TAOS) from individual flowing biological aerosol particles. The fluorescence spectra have been observed from more than 20 samples including Bacillus subtilis, Escherichia coli, Erwinia herbicola, allergens, dust, and smoke. The S/N and resolution of the spectra are sufficient for observing small lineshape differences among the same type of bioaerosol prepared under different conditions. The additional information from TAOS regarding particle size, shape, and granularity has the potential of aiding in distinguishing bacterial aerosols from other aerosols, such as diesel and cigarette smoke.

  15. Material/element-dependent fluorescence-yield modes on soft X-ray absorption spectroscopy of cathode materials for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Asakura, Daisuke; Hosono, Eiji; Nanba, Yusuke; Zhou, Haoshen; Okabayashi, Jun; Ban, Chunmei; Glans, Per-Anders; Guo, Jinghua; Mizokawa, Takashi; Chen, Gang; Achkar, Andrew J.; Hawthron, David G.; Regier, Thomas Z.; Wadati, Hiroki

    2016-03-01

    We evaluate the utilities of fluorescence-yield (FY) modes in soft X-ray absorption spectroscopy (XAS) of several cathode materials for Li-ion batteries. In the case of total-FY (TFY) XAS for LiNi0.5Mn1.5O4, the line shape of the Mn L3-edge XAS was largely distorted by the self-absorption and saturation effects, while the distortions were less pronounced at the Ni L3 edge. The distortions were suppressed for the inverse-partial-FY (IPFY) spectra. We found that, in the cathode materials, the IPFY XAS is highly effective for the Cr, Mn, and Fe L edges and the TFY and PFY modes are useful enough for the Ni L edge which is far from the O K edge.

  16. X-ray fluorescence and absorption analysis of krypton in irradiated nuclear fuel

    NASA Astrophysics Data System (ADS)

    Degueldre, Claude; Mieszczynski, Cyprian; Borca, Camelia; Grolimund, Daniel; Martin, Matthias; Bertsch, Johannes

    2014-10-01

    The analysis of krypton in irradiated uranium dioxide fuel has been successfully achieved by X-ray fluorescence and X-ray absorption. The present study focuses on the analytical challenge of sample and sub-sample production to perform the analysis with the restricted conditions dictated by the radioprotection regulations. It deals also with all potential interferences that could affect the quality of the measurement in fluorescence as well as in absorption mode. The impacts of all dissolved gases in the fuel matrix are accounted for the analytical result quantification. The krypton atomic environment is ruled by the presence of xenon. Other gases such as residual argon and traces of helium or hydrogen are negligible. The results are given in term of density for krypton (∼3 nm-3) and xenon (∼20 nm-3). The presence of dissolved, interstitial and nano-phases are discussed together with other analytical techniques that could be applied to gain information on fission gas behaviour in nuclear fuels.

  17. Single particle size and fluorescence spectra from emissions of burning materials in a tube furnace to simulate burn pits

    NASA Astrophysics Data System (ADS)

    Pan, Yong-Le; Houck, Joshua D. T.; Clark, Pamela A.; Pinnick, Ronald G.

    2013-08-01

    A single-particle fluorescence spectrometer (SPFS) and an aerodynamic particle sizer were used to measure the fluorescence spectra and particle size distribution from the particulate emissions of 12 different burning materials in a tube furnace to simulate open-air burning of garbage. Although the particulate emissions are likely dominated by particles <1 μm diameter, only the spectra of supermicron particles were measured here. The overall fluorescence spectral profiles exhibit either one or two broad bands peaked around 300-450 nm within the 280-650 nm spectral range, when the particles are illuminated with a 263-nm laser. Different burning materials have different profiles, some of them (cigarette, hair, uniform, paper, and plastics) show small changes during the burning process, and while others (beef, bread, carrot, Styrofoam, and wood) show big variations, which initially exhibit a single UV peak (around 310-340 nm) and a long shoulder in visible, and then gradually evolve into a bimodal spectrum with another visible peak (around 430-450 nm) having increasing intensity during the burning process. These spectral profiles could mainly derive from polycyclic aromatic hydrocarbons with the combinations of tyrosine-like, tryptophan-like, and other humic-like substances. About 68 % of these single-particle fluorescence spectra can be grouped into 10 clustered spectral templates that are derived from the spectra of millions of atmospheric aerosol particles observed in three locations; while the others, particularly these bimodal spectra, do not fall into any of the 10 templates. Therefore, the spectra from particulate emissions of burning materials can be easily discriminated from that of common atmospheric aerosol particles. The SFFS technology could be a good tool for monitoring burning pit emissions and possibly for distinguishing them from atmospheric aerosol particles.

  18. Inspecting absorption in the spectra of extra-galactic gamma-ray sources for insight into Lorentz invariance violation

    SciTech Connect

    Jacob, Uri; Piran, Tsvi

    2008-12-15

    We examine what the absorbed spectra of extra-galactic TeV gamma-ray sources, such as blazars, would look like in the presence of Lorentz invariance violation. Pair production with the extra-galactic background light modifies the observed spectra of such sources, and we show that a violation of Lorentz invariance would generically have a dramatic effect on this absorption feature. Inspecting this effect, an experimental task likely practical in the near future, can provide unique insight on the possibility of Lorentz invariance violation.

  19. Near-infrared absorption spectra of C{sub 60} radical cations and anions prepared simultaneously in solid argon

    SciTech Connect

    Gasyna, Z.; Andrews, L.; Schatz, P.N.

    1992-02-20

    The codeposition of C{sub 60} vapor with excess argon and argon resonance radiation has produced strong new absorptions at 973 and 1068 nm in solid argon at 11 {+-} 1 K. A similar experiment with CCl{sub 4} added to serve as an electron trap reduced the yield of the 1068-nm band with little effect on the 973-nm absorption. The 973-nm band is assigned to C{sub 60}{sup {sm_bullet}+} produced by photoionization and the 1068-nm band to C{sub 60}{sup {sm_bullet}-} formed by electron capture. These identifications are in excellent agreement with glassy matrix, solution, and photoelectron spectra.

  20. Double photoexcitation involving 2p and 4f electrons in L3 -edge x-ray absorption spectra of protactinium

    NASA Astrophysics Data System (ADS)

    Hennig, Christoph; Le Naour, Claire; Auwer, Christophe Den

    2008-06-01

    The L3 -edge x-ray absorption spectrum of Pa(V) fluoride in aqueous solution show clear evidence for the double photoexcitation involving 2p and 4f electrons. A comparison with the [2p4f] double-electron excitations observed in the L3 -edge x-ray absorption spectra of other actinides (thorium, uranium, neptunium, plutonium, and americium) indicates a monotonic increase in the excitation energy. The sharp edgelike structure of the multielectron excitation reveals the origin of a shake-up channel.

  1. A Study of the Ultraviolet Absorptions in the Spectra of DA White Dwarfs and Ultraviolet Spectra of the Star HR6560

    NASA Technical Reports Server (NTRS)

    Wegner, Gary A.

    1986-01-01

    Two projects in conjunction with the International Ultraviolet Explorer Satellite are discussed. These projects were to: (1) study the properties of the H2 and H2+ quasi-molecular absorption features at lambda lambda 1600 and 1400 in the ultraviolet spectra of the hydrogen-rich DA white dwarfs and to search for additional spectroscopic features in the spectra of these stars; and (2) use the ultraviolet portion of the spectrum of the peculiar rare earth-rich late F type star, HR6560 (HD159870), to establish whether or not the element abundance anomalies are produced in conjunction with its having a white dwarf binary companion. The data show that HR6560 is probably not associated with any hot subluminous or degenerate star.

  2. Spectral fluorescence signature techniques and absorption measurements for continuous monitoring of biofuel-producing microalgae cultures

    NASA Astrophysics Data System (ADS)

    Martín de la Cruz, M. C.; Gonzalez Vilas, L.; Yarovenko, N.; Spyrakos, E.; Torres Palenzuela, J. M.

    2013-08-01

    Biofuel production from microalgae can be both sustainable and economically viable. Particularly in the case of algal growth in wastewater an extra benefit is the removal or biotransformation of pollutants from these types of waters. A continuous monitoring system of the microalgae status and the concentration of different wastewater contaminants could be of great help in the biomass production and the water characterisation. In this study we present a system where spectral fluorescence signature (SFS) techniques are used along with absorption measurements to monitor microalgae cultures in wastewater and other mediums. This system aims to optimise the microalgae production for biofuel applications or other uses and was developed and tested in prototype indoor photo-bioreactors at the University of Vigo. SFS techniques were applied using the fluorescence analyser INSTAND-SCREENER developed by Laser Diagnostic Instruments AS. INSTAND-SCREENER permits wavelength scanning in two modes, one in UV and another in VIS. In parallel, it permits the on-line monitoring and rapid analysis of both water quality and phytoplankton status without prior treatment of the sample. Considering that different contaminants and microalgae features (density, status etc.) have different spectral signatures of fluorescence and absorption properties, it is possible to characterise them developing classification libraries. Several algorithms were used for the classification. The implementation of this system in an outdoor raceway reactor in a Spanish wastewater treatment plant is also discussed. This study was part of the Project EnerBioAlgae (http://www.enerbioalgae.com/), which was funded by the Interreg SUDOE and led by the University of Vigo.

  3. Determination of mercury distribution inside spent compact fluorescent lamps by atomic absorption spectrometry.

    PubMed

    Rey-Raap, Natalia; Gallardo, Antonio

    2012-05-01

    In this study, spent compact fluorescent lamps were characterized to determine the distribution of mercury. The procedure used in this research allowed mercury to be extracted in the vapor phase, from the phosphor powder, and the glass matrix. Mercury concentration in the three phases was determined by the method known as cold vapor atomic absorption spectrometry. Median values obtained in the study showed that a compact fluorescent lamp contained 24.52±0.4ppb of mercury in the vapor phase, 204.16±8.9ppb of mercury in the phosphor powder, and 18.74±0.5ppb of mercury in the glass matrix. There are differences in mercury concentration between the lamps since the year of manufacture or the hours of operation affect both mercury content and its distribution. The 85.76% of the mercury introduced into a compact fluorescent lamp becomes a component of the phosphor powder, while more than 13.66% is diffused through the glass matrix. By washing and eliminating all phosphor powder attached to the glass surface it is possible to classified the glass as a non-hazardous waste.

  4. Absorption and fluorescence of hydrophobic components of dissolved organic matter in several Karelian lakes with stratified structures

    NASA Astrophysics Data System (ADS)

    Khundzhua, Daria A.; Kharcheva, Anastasia V.; Krasnova, Elena D.; Gorshkova, Olga M.; Chevel, Kira A.; Yuzhakov, Viktor I.; Patsaeva, Svetlana V.

    2016-04-01

    Hydrophobic components of cromophoric dissolved organic matter (CDOM) extracted from water samples and sediments taken in several relic basins located on Karelian shoreline of the White Sea were analyzed using spectroscopic techniques. Those water reservoirs exist at various stages of isolation from the White Sea and represent complex stratified systems of fresh and marine water layers not completely mixing trough the year. Basins separating from the White Sea are the unique natural objects for investigations of properties CDOM, its transformation in the process of turning the marine ecosystem into freshwater environment. CDOM occurring in all types of natural water represents a significant reservoir of organic carbon and plays a key role in the carbon cycle on the Earth. However, aquatic CDOM and nonliving organic matter in sediments from relic separating basins still have not been studied. The target of this work was to study absorption and fluorescence spectra of hydrophobic components of aquatic CDOM from different water depth and sediments in several separated basins of the Kandalaksha Gulf of the White Sea located near the N.A. Pertsov White Sea Biological Station.

  5. First-principles calculation of principal Hugoniot and K-shell X-ray absorption spectra for warm dense KCl

    SciTech Connect

    Zhao, Shijun; Zhang, Shen; Kang, Wei; Li, Zi; Zhang, Ping; He, Xian-Tu

    2015-06-15

    Principal Hugoniot and K-shell X-ray absorption spectra of warm dense KCl are calculated using the first-principles molecular dynamics (FPMD) method. Evolution of electronic structures as well as the influence of the approximate description of ionization on pressure (caused by the underestimation of the energy gap between conduction bands and valence bands) in the first-principles method are illustrated by the calculation. It is shown that approximate description of ionization in FPMD has small influence on Hugoniot pressure due to mutual compensation of electronic kinetic pressure and virial pressure. The calculation of X-ray absorption spectra shows that the band gap of KCl persists after the pressure ionization of the 3p electrons of Cl and K taking place at lower energy, which provides a detailed understanding to the evolution of electronic structures of warm dense matter.

  6. Near infrared absorption spectra of C{sub 60} radical cations and anions prepared simultaneously in solid argon

    SciTech Connect

    Schatz, P.N.; Gasyna, Z.; Andrews, L.

    1992-12-01

    The codeposition of C{sub 60} vapor with excess argon and concurrent argon resonance radiation has produced strong new absorptions at 973 and 1068 nm in solid argon at 11 {plus_minus} 1 K. A similar experiment with CCl{sub 4}, added to serve as an electron trap, reduced the yield of the 1068 nm band with little effect on the 973 nm absorption. The 973 nm band is assigned to C{sub 60}{sup +} produced by photoionization and the 1068 nm band to C{sub 60}{sup {minus}} formed by electron capture. These identifications are in excellent agreement with glassy matrix, solution and photoelectron spectra. Preliminary magnetic circular dichroism (MCD) spectra of the 973 nm C{sub 60}{sup +} band have also been measured. Both the 1068 and 973 nm bands show a characteristic triplet structure which is tentatively attributed to the combined effects of spin-orbit and Jahn-Teller coupling.

  7. Potential chlorofluorocarbon replacements: OH reaction rate constants between 250 and 315 K and infrared absorption spectra

    SciTech Connect

    Garland, N.L.; Medhurst, L.J.; Nelson, H.H.

    1993-12-20

    The authors measured the rate constant for reactions of the OH radical with several potential chlorofluorocarbon replacements over the temperature range 251-314 K using laser photolysis laser-induced fluorescence techniques. The compounds studied and Arrhenius parameters determined from fits to the measured rate constants are as follows: CHF{sub 2}OCHF{sub 2} (E 134), k(T) = (5.4 {+-} 3.5) x 10{sup {minus}13} cm{sup 3} s{sup {minus}1} exp [({minus}3.1 {+-} 0.4 kcal mol{sup {minus}1})/RT]; CF{sub 3}CH{sub 2}CF{sub 3} (FC 236fa), k(T) = (2.0 {+-} 1.0) x 10{sup {minus}14} cm{sup 3} s{sup {minus}1} exp [({minus}1.8 {+-} 0.3 kcal mol{sup {minus}1})/RT]; CF{sub 3}CHFCHF{sub 2} (FC 236ea), k(T) = (2.0 {+-} 0.9) x 10{sup {minus}13} cm{sup 3} s{sup {minus}1} exp [({minus}2.0 {+-} 0.3 kcal mol{sup {minus}1})/RT]; and CF{sub 3}CF{sub 2}CH{sub 2}F (FC 236cb), k(T) = (2.6 {+-} 1.6) x 10{sup {minus}13} cm{sup 3} s{sup {minus}1} exp [({minus}2.2 {+-} 0.4 kcal mol{sup {minus}1})/RT]. The measured activation energies (2-3 kcal mol{sup {minus}1}) are consistent with a mechanism of H atom abstraction. The tropospheric lifetimes, estimated from the measured OH reaction rates, and measured integrated infrared absorption cross sections over the range 770 to 1430 cm{sup {minus}1} suggest that E 134 and FC 236fa may have significant global warming potential, while FC 236ea and FC 236cb do not. 17 refs., 4 figs., 3 tabs.

  8. Near infrared excited micro-Raman spectra of 4:1 methanol-ethanol mixture and ruby fluorescence at high pressure

    NASA Astrophysics Data System (ADS)

    Wang, X. B.; Shen, Z. X.; Tang, S. H.; Kuok, M. H.

    1999-06-01

    Near infrared (NIR) lasers, as a new excitation source for Raman spectroscopy, has shown its unique advantages and is being increasingly used for some special samples, such as those emitting strong fluorescence in the visible region. This article focuses on some issues related to high-pressure micro-Raman spectroscopy using NIR excitation source. The Raman spectra of 4:1 methanol-ethanol mixture (4:1 M-E) show a linear variation in both Raman shifts and linewidths under pressure up to 18 GPa. This result is useful in distinguishing Raman scattering of samples from that of the alcohol mixture, an extensively used pressure-transmitting medium. The R1 fluorescence in the red region induced by two-photon absorption of the NIR laser is strong enough to be used as pressure scale. The frequency and line width of the R1 lines are very sensitive to pressure change and the glass transition of the pressure medium. Our results manifest that it is reliable and convenient to use NIR induced two-photon excited fluorescence of ruby for both pressure calibration and distribution of pressure in the 4:1 M-E pressure transmitting medium.

  9. Absorption and fluorescence emission spectroscopic characters of naphtho-homologated yy-DNA bases and effect of methanol solution and base pairing.

    PubMed

    Zhang, Laibin; Li, Huifang; Li, Jilai; Chen, Xiaohua; Bu, Yuxiang

    2010-03-01

    A comprehensive theoretical study of electronic transitions of naphtho-homologated base analogs, namely, yy-T, yy-C, yy-A, and yy-G, was performed. The nature of the low-lying excited states is discussed, and the results are compared with those from experiment and also with those of y-bases. Geometrical characteristics of the lowest excited singlet pipi* and npi* states were explored using the CIS method, and the effects of methanol solution and paring with their complementary natural bases on the relevant absorption and emission spectra of these modified bases were examined. The calculated excitation and emission energies agree well with the measured data, where experimental results are available. In methanol solution, the fluorescence from yy-A and yy-G would be expected to occur around 539 and 562 nm, respectively, suggesting that yy-A is a green-colored fluorophore, whereas yy-G is a yellow-colored fluorophore. The methanol solution was found to red-shift both the absorption and emission maxima of yy-A, yy-T, and yy-C, but blue-shift those for yy-G. Generally, though base pairing has no significant effects on the absorption and fluorescence maxima of yy-A, yy-C, and yy-T, it blue-shifts those for yy-G.

  10. Recalibration of the absorption/photodissociation spectra of CO and its isotopes between 91 and 115 nm

    NASA Technical Reports Server (NTRS)

    Eidelsberg, M.; Benayoun, J. J.; Viala, Y.; Rostas, F.; Smith, P. L.; Yoshino, K.; Stark, G.; Shettle, C. A.

    1992-01-01

    A systematic error has been identified in the wavelengths and wavenumbers presented in two papers concerning the absorption/dissociation spectra of CO and isotopes between 91.2 and 115.2 nm. The published wavelengths are about 10 mA (0.001 nm) too small for lines in the 91-100 nm range. A table of corrected band origins is provided.

  11. Features in optical absorption and photocurrent spectra of organic solar cells due to organic/organic interface

    NASA Astrophysics Data System (ADS)

    Ismail, Yasser A. M.; Soga, Tetsuo; Jimbo, Takashi

    2011-05-01

    We surprisingly found that, organic/organic interface had a direct and pronounced impact on optical absorption and photocurrent spectra of organic solar cell at a favorable wavelength region of the visible solar spectrum. The organic/organic interface was formed as a result of connection between coumarin 6 (C6): [6,6]-phenyl-C61 butyric acid methyl ester (PCBM) blend films and indium-tin oxide (ITO)/poly(3,4-ethylenedioxythiophene) doped with poly(styrene sulfonate) (PEDOT:PSS) electrode. Optical absorption measurement was carried out for ITO/PEDOT:PSS/C6:PCBM films, while external quantum efficiency measurement was carried out for ITO/PEDOT:PSS/C6:PCBM/Al solar cells, with varying C6:PCBM blend concentration. We found that, the C6:PCBM blend in the ITO/PEDOT:PSS/C6:PCBM films had an additional feature in the absorption spectra at the wavelength range of 520-800 nm, at which the C6 dye, PCBM, PEDOT:PSS, and ITO were transparent. An additional feature, also, appeared in photocurrent spectra of the C6:PCBM films in the ITO/PEDOT:PSS/C6:PCBM/Al solar cells at the same wavelength range. The new features in the optical absorption and photocurrent spectra of the investigated solar cells originated, in all probability, due to optically induced sup-band transitions in the C6:PCBM blend films at the interface with ITO/PEDOT:PSS electrode. Thus, the C6:PCBM blend films produced a charge carrier generation interface due to connection with ITO/PEDOT:PSS electrode. As a result of this charge carrier generation interface, the power conversion efficiency of the corresponding solar cell is improved. Taking into consideration these new findings, the high-band-gap organic materials will take more importance as sensitizers in organic optoelectronic applications.

  12. Interacting He and Ar atoms: Revised theoretical interaction potential, dipole moment, and collision-induced absorption spectra

    SciTech Connect

    Meyer, Wilfried; Frommhold, Lothar

    2015-09-21

    Coupled cluster quantum chemical calculations of the potential energy surface and the induced dipole surface are reported for the He–Ar van der Waals collisional complex. Spectroscopic parameters are derived from global analytical fits while an accurate value for the long-range dipole coefficient D{sub 7} is obtained by perturbation methods. Collision-induced absorption spectra are computed quantum mechanically and compared with existing measurements.

  13. Conformational effects in the absorption spectra and photochemistry of [2, n](9,10)anthracenophanes ( n = 2,3)

    NASA Astrophysics Data System (ADS)

    Dunand, Albert; Ferguson, James; Puza, Miroslav; Robertson, Glen B.

    1980-11-01

    The absorption spectra of [2.2](9,10)anthracenophane (1) and [2.3](9,10)anthracenophane (II), in condensed media, contain overlapping contributions from two conformational isomers with quite different spectra. The spectra of the two conformations of I and of one conformation of II have been separately determined by a solid state method. This involved the incorporation of the photoisomers of I (1,2,7,8,-tetrahydro-2a,6b[1',2']:8a, 12b[1″,2″] -dibenzenodibenzo [a,c] dicyclo- buta[e.g]cyclooctene) and II (1,2,8,9-tetrahydro-2a,6b[1',2']:9a,13b[1″,2″]-dibenzeno-7H-dibenzo[a,e]cyclobuta[c]-cyclopenta[g]cyclooctene) in host single crystals of the photoisomer of 1,3-di(9-anthryl)propane, I and II were then obtained by thermal dissociation and their spectra measured at 8 K. The two conformers of 1 were separated by photoselection, the rotated conformer being between 4 and 5 times more photoreactive than the translated conformer. A modified molecular force field program was used to simulate the environment around the guest molecule (I) and the resultant geometries and orientations in the (disordered) site of the host crystal are in excellent agreement with the polarization analysis of the absorption spectra. Two crystal orientations of the rotated conformer were found. For II, the rotated conformation, with two orientations, dominates the absorption spectrum and the translated conformer could not be obtained by photoselection. The force field program was used to calculate the molecular geometries (gas phase) of both conformations of I and II and their photoisomers, I was also obtained by ultraviolet photodissociation of its photoisomer at 8 K. Both conformers were obtained with the same ratio as for the thermally treated crystals. This result considered with the photoselection experiments, demonstrates that the reversible photoisomerization does not proceed via biradical intermediate.

  14. Research program in nuclear and solid state physics. [including pion absorption spectra and muon spin precession

    NASA Technical Reports Server (NTRS)

    1974-01-01

    The survey of negative pion absorption reactions on light and medium nuclei was continued. Muon spin precession was studied using an iron target. An impulse approximation model of the pion absorption process implied that the ion will absorb almost exclusively on nucleon pairs, single nucleon absorption being suppressed by energy and momentum conservation requirements. For measurements on both paramagnetic and ferromagnetic iron, the external magnetic field was supplied by a large C-type electromagnet carrying a current of about 100 amperes.

  15. Application of Video Spectral Comparator (absorption spectra) for establishing the chronological order of intersecting printed strokes and writing pen strokes.

    PubMed

    Kaur, Ridamjeet; Saini, Komal; Sood, N C

    2013-06-01

    The sequence of intersecting strokes of laser printers (black, blue, red and green) and typewriter ink (black) with the strokes of gel pen ink, ballpoint pen ink and fountain pen ink (black, blue, red and green) has been determined by studying their absorption spectra. The absorption spectra have been generated for each of the two pure inks (i.e. A and B) and points of their intersections (i.e. A over B and B over A) by using Video Spectral Comparator (VSC-2000-HR). The study was carried out with an assumption that the peak characteristics of spectra from the point of intersection should correspond to the peak characteristics of pure ink which was executed later. It was observed that the absorption spectrum of intersection corresponds with either the laser printer or the typewriter ink stroke, whether these strokes were executed earlier or later than the writing instrument strokes. As the results obtained from the study were negative, the FDEs are advised against the practice of this technique in the examination of the sequence of intersecting strokes for these specified inks. PMID:23601731

  16. Application of Video Spectral Comparator (absorption spectra) for establishing the chronological order of intersecting printed strokes and writing pen strokes.

    PubMed

    Kaur, Ridamjeet; Saini, Komal; Sood, N C

    2013-06-01

    The sequence of intersecting strokes of laser printers (black, blue, red and green) and typewriter ink (black) with the strokes of gel pen ink, ballpoint pen ink and fountain pen ink (black, blue, red and green) has been determined by studying their absorption spectra. The absorption spectra have been generated for each of the two pure inks (i.e. A and B) and points of their intersections (i.e. A over B and B over A) by using Video Spectral Comparator (VSC-2000-HR). The study was carried out with an assumption that the peak characteristics of spectra from the point of intersection should correspond to the peak characteristics of pure ink which was executed later. It was observed that the absorption spectrum of intersection corresponds with either the laser printer or the typewriter ink stroke, whether these strokes were executed earlier or later than the writing instrument strokes. As the results obtained from the study were negative, the FDEs are advised against the practice of this technique in the examination of the sequence of intersecting strokes for these specified inks.

  17. Electronic structure of some adenosine receptor antagonists. III. Quantitative investigation of the electronic absorption spectra of alkyl xanthines

    NASA Astrophysics Data System (ADS)

    Moustafa, H.; Shalaby, Samia H.; El-sawy, K. M.; Hilal, Rifaat

    2002-07-01

    Quantitative and comparative investigation of the electronic absorption spectra of theophylline, caffeine and their derivatives is reported. The spectra of theophylline, caffeine and theobromine were compared to establish the predominant tautomeric species in solution. This comparison, analysis of solvent effects and assignments of the observed transitions via MO computations indicate the exits of only one tautomeric species in solution that is the N7 form. A low-lying triplet state was identified which corresponds to a HOMO-LUMO transition. This relatively long-lived T 1 state is always less polar than the ground state and may very well underlie the photochemical reactivity of alkyl xanthines. Substituents of different electron donating or withdrawing strengths and solvent effects are investigated and analyzed. The present analysis is facilitated via computer deconvolution of the observed spectra and MO computation.

  18. Förster resonance energy transfer, absorption and emission spectra in multichromophoric systems. III. Exact stochastic path integral evaluation

    SciTech Connect

    Moix, Jeremy M.; Ma, Jian; Cao, Jianshu

    2015-03-07

    A numerically exact path integral treatment of the absorption and emission spectra of open quantum systems is presented that requires only the straightforward solution of a stochastic differential equation. The approach converges rapidly enabling the calculation of spectra of large excitonic systems across the complete range of system parameters and for arbitrary bath spectral densities. With the numerically exact absorption and emission operators, one can also immediately compute energy transfer rates using the multi-chromophoric Förster resonant energy transfer formalism. Benchmark calculations on the emission spectra of two level systems are presented demonstrating the efficacy of the stochastic approach. This is followed by calculations of the energy transfer rates between two weakly coupled dimer systems as a function of temperature and system-bath coupling strength. It is shown that the recently developed hybrid cumulant expansion (see Paper II) is the only perturbative method capable of generating uniformly reliable energy transfer rates and emission spectra across a broad range of system parameters.

  19. Characterizing the Structures, Spectra, and Energy Landscapes Involved in the Excited-State Proton Transfer Process of Red Fluorescent Protein LSSmKate1.

    PubMed

    Chen, Fasheng; Zeng, Qiao; Zhuang, Wei; Liang, WanZhen

    2016-09-22

    By applying molecular dynamics (MD) simulations and quantum chemical calculations, we have characterized the states and processes involved in the excited-state proton transfer (ESPT) of LSSmKate1. MD simulations identify two stable structures in the electronic ground state of LSSmKate1, one with a protonated chromophore and the other with a deprotonated chromophore, thus leading to two separate low-energy absorption maxima with a large energy spacing, as observed in the calculated and experimentally measured absorption spectra. Proton transfer is induced by electronic excitation. When LSSmKate1 is excited, the electrons in the chromophore are transferred from the phenol ring to the N-acylimine moiety; the acidity of a phenolic hydroxyl group is thus enhanced. The calculated potential energy curves (PECs) exhibit energetic feasibility in the generation of the fluorescent species in LSSmKate1, and the exact agreement between the calculated and experimentally measured values of the large Stokes shift further provides solid theoretical evidence for the ESPT process taking place in photoexcited LSSmKate1. The molecular environments play a significant role in the geometries and absorption/emission energies of the chromophores. Overall, TD-ωB97X-D/molecular mechanics (MM) provides a better description of the optical properties of LSSmKate1 than TD-B3LYP/MM, although it always overestimates the excitation energies. PMID:27581731

  20. Characterizing the Structures, Spectra, and Energy Landscapes Involved in the Excited-State Proton Transfer Process of Red Fluorescent Protein LSSmKate1.

    PubMed

    Chen, Fasheng; Zeng, Qiao; Zhuang, Wei; Liang, WanZhen

    2016-09-22

    By applying molecular dynamics (MD) simulations and quantum chemical calculations, we have characterized the states and processes involved in the excited-state proton transfer (ESPT) of LSSmKate1. MD simulations identify two stable structures in the electronic ground state of LSSmKate1, one with a protonated chromophore and the other with a deprotonated chromophore, thus leading to two separate low-energy absorption maxima with a large energy spacing, as observed in the calculated and experimentally measured absorption spectra. Proton transfer is induced by electronic excitation. When LSSmKate1 is excited, the electrons in the chromophore are transferred from the phenol ring to the N-acylimine moiety; the acidity of a phenolic hydroxyl group is thus enhanced. The calculated potential energy curves (PECs) exhibit energetic feasibility in the generation of the fluorescent species in LSSmKate1, and the exact agreement between the calculated and experimentally measured values of the large Stokes shift further provides solid theoretical evidence for the ESPT process taking place in photoexcited LSSmKate1. The molecular environments play a significant role in the geometries and absorption/emission energies of the chromophores. Overall, TD-ωB97X-D/molecular mechanics (MM) provides a better description of the optical properties of LSSmKate1 than TD-B3LYP/MM, although it always overestimates the excitation energies.

  1. Searching for narrow absorption and emission lines in XMM-Newton spectra of gamma-ray bursts

    NASA Astrophysics Data System (ADS)

    Campana, S.; Braito, V.; D'Avanzo, P.; Ghirlanda, G.; Melandri, A.; Pescalli, A.; Salafia, O. S.; Salvaterra, R.; Tagliaferri, G.; Vergani, S. D.

    2016-08-01

    We present the results of a spectroscopic search for narrow emission and absorption features in the X-ray spectra of long gamma-ray burst (GRB) afterglows. Using XMM-Newton data, both EPIC and RGS spectra, of six bright (fluence > 10-7 erg cm-2) and relatively nearby (z = 0.54-1.41) GRBs, we performed a blind search for emission or absorption lines that could be related to a high cloud density or metal-rich gas in the environ close to the GRBs. We detected five emission features in four of the six GRBs with an overall statistical significance, assessed through Monte Carlo simulations, of ≲ 3.0σ. Most of the lines are detected around the observed energy of the oxygen edge at ~ 0.5 keV, suggesting that they are not related to the GRB environment but are most likely of Galactic origin. No significant absorption features were detected. A spectral fitting with a free Galactic column density (NH) testing different models for the Galactic absorption confirms this origin because we found an indication of an excess of Galactic NH in these four GRBs with respect to the tabulated values.

  2. Flow cytometric analysis of cellular endogenous fluorescence simultaneously with emission from exogenous fluorochromes, light scatter and absorption

    SciTech Connect

    Thorell, B.

    1981-07-01

    A cytofluorimeter capable of simultaneous 4-parameter analysis (i.e., endogenous fluorescence (NAD(P)H), exogenous fluorescent dyes, absorption and small angle scatter) is described. Analyses have been performed on isolated rat liver cells, white blood cells, bone marrow, thymus cells and yeast under different metabolic states. This allows correlations between cell function and concentration of cell substances, size, refractive indices, etc. Kinetic measurements are also possible.

  3. Absorption, fluorescence, and acid-base equilibria of rhodamines in micellar media of sodium dodecyl sulfate.

    PubMed

    Obukhova, Elena N; Mchedlov-Petrossyan, Nikolay O; Vodolazkaya, Natalya A; Patsenker, Leonid D; Doroshenko, Andrey O; Marynin, Andriy I; Krasovitskii, Boris M

    2017-01-01

    Rhodamine dyes are widely used as molecular probes in different fields of science. The aim of this paper was to ascertain to what extent the structural peculiarities of the compounds influence their absorption, emission, and acid-base properties under unified conditions. The acid-base dissociation (HR(+)⇄R+H(+)) of a series of rhodamine dyes was studied in sodium n-dodecylsulfate micellar solutions. In this media, the form R exists as a zwitterion R(±). The indices of apparent ionization constants of fifteen rhodamine cations HR(+) with different substituents in the xanthene moiety vary within the range of pKa(app)=5.04 to 5.53. The distinct dependence of emission of rhodamines bound to micelles on pH of bulk water opens the possibility of using them as fluorescent interfacial acid-base indicators.

  4. Invited Review Article: Imaging techniques for harmonic and multiphoton absorption fluorescence microscopy

    PubMed Central

    Carriles, Ramón; Schafer, Dawn N.; Sheetz, Kraig E.; Field, Jeffrey J.; Cisek, Richard; Barzda, Virginijus; Sylvester, Anne W.; Squier, Jeffrey A.

    2009-01-01

    We review the current state of multiphoton microscopy. In particular, the requirements and limitations associated with high-speed multiphoton imaging are considered. A description of the different scanning technologies such as line scan, multifoci approaches, multidepth microscopy, and novel detection techniques is given. The main nonlinear optical contrast mechanisms employed in microscopy are reviewed, namely, multiphoton excitation fluorescence, second harmonic generation, and third harmonic generation. Techniques for optimizing these nonlinear mechanisms through a careful measurement of the spatial and temporal characteristics of the focal volume are discussed, and a brief summary of photobleaching effects is provided. Finally, we consider three new applications of multiphoton microscopy: nonlinear imaging in microfluidics as applied to chemical analysis and the use of two-photon absorption and self-phase modulation as contrast mechanisms applied to imaging problems in the medical sciences. PMID:19725639

  5. Synchrotron x-ray fluorescence and extended x-ray absorption fine structure analysis

    SciTech Connect

    Chen, J.R.; Gordon, B.M.; Hanson, A.L.; Jones, K.W.; Kraner, H.W.; Chao, E.C.T.; Minkin, J.A.

    1984-01-01

    The advent of dedicated synchrotron radiation sources has led to a significant increase in activity in many areas of science dealing with the interaction of x-rays with matter. Synchrotron radiation provides intense, linearly polarized, naturally collimated, continuously tunable photon beams, which are used to determine not only the elemental composition of a complex, polyatomic, dilute material but also the chemical form of the elements with improved accuracy. Examples of the application of synchrotron radiation include experiments in synchrotron x-ray fluorescence (SXRF) analysis and extended x-ray absorption fine structure (EXAFS) analysis. New synchrotron radiation x-ray microprobes for elemental analysis in the parts per billion range are under construction at several laboratories. 76 references, 24 figures.

  6. Absorption, fluorescence, and acid-base equilibria of rhodamines in micellar media of sodium dodecyl sulfate.

    PubMed

    Obukhova, Elena N; Mchedlov-Petrossyan, Nikolay O; Vodolazkaya, Natalya A; Patsenker, Leonid D; Doroshenko, Andrey O; Marynin, Andriy I; Krasovitskii, Boris M

    2017-01-01

    Rhodamine dyes are widely used as molecular probes in different fields of science. The aim of this paper was to ascertain to what extent the structural peculiarities of the compounds influence their absorption, emission, and acid-base properties under unified conditions. The acid-base dissociation (HR(+)⇄R+H(+)) of a series of rhodamine dyes was studied in sodium n-dodecylsulfate micellar solutions. In this media, the form R exists as a zwitterion R(±). The indices of apparent ionization constants of fifteen rhodamine cations HR(+) with different substituents in the xanthene moiety vary within the range of pKa(app)=5.04 to 5.53. The distinct dependence of emission of rhodamines bound to micelles on pH of bulk water opens the possibility of using them as fluorescent interfacial acid-base indicators. PMID:27423469

  7. Excitations, optical absorption spectra, and optical excitonic gaps of heterofullerenes: I. C60, C59N+ and C48N12

    SciTech Connect

    Xie, R; Bryant, G W; Sun, G; C.Nicklaus, M; Heringer, D; Frauenheim, T; Manaa, M R; Smith, Jr., V H; Araki, Y; Ito, O

    2003-10-02

    Low-energy excitations and optical absorption spectrum of C{sub 60} are computed by using time-dependent (TD) Hartree-Fock (HF), TD-density functional theory (TD-DFT), TD-DFT-based tight-binding (TD-DFT-TB) and a semiempirical ZINDO method. A detailed comparison of experiment and theory for the excitation energies, optical gap and absorption spectrum of C{sub 60} is presented. It is found that electron correlations and collective effects of exciton pairs play important roles in assigning accurately the spectral features of C{sub 60} and the TD-DFT method with non-hybrid functionals or a local spin density approximation leads to more accurate excitation energies than with hybrid functionals. The level of agreement between theory and experiment for C{sub 60} justifies similar calculations of the excitations and optical absorption spectrum of a monomeric azafullerene cation C{sub 59}N{sup +} exhibits distinguishing spectral features different from C{sub 60}: (1) the first singlet is dipole-allowed and the optical gap is redshifted by 1.44 eV; (2) several weaker absorption maxima occur in the visible region; (3) the transient triplet-triplet absorption at 1.60 eV (775 nm) is much broader and the decay of the triplet state is much faster. The calculated spectra of C{sub 59}N{sup +} characterize and explain well our measured ultraviolet-visible (UV-vis) and transient absorption spectra of the carborane anion salt [C{sub 59}N][Ag(CB{sub 11}H{sub 6}Cl{sub 6}){sub 2}]. For the most stable isomer of C{sub 48}N{sub 12}, we predict that the first singlet is dipole-allowed, the optical gap is redshifted by 1.22 eV relative to that of C{sub 60}, and optical absorption maxima occur at 585, 528, 443, 363, 340, 314 and 303 nm. We point out that the characterization of the UV-vis and transient absorption spectra of C{sub 48}N{sub 12} isomers is helpful in distinguishing the isomer structures required for applications in molecular electronics. For C{sub 59}N{sup +} and C{sub 48}N

  8. Computed and Experimental Absorption Spectra of the Perovskite CH3NH3PbI3.

    PubMed

    Zhu, Xi; Su, Haibin; Marcus, Rudolph A; Michel-Beyerle, Maria E

    2014-09-01

    Electronic structure and light absorption properties of the perovskite CH3NH3PbI3 are investigated by relativistic density functional theory with quasiparticle GW corrections and many-body interactions. The nature of the Wannier exciton is studied by solving the Bethe-Salpeter equation augmented with the analysis of a conceptual hydrogen-like model. The computed absorption spectrum unravels a remarkable absorption "gap" between the first two absorption peaks. This discontinuity is maintained in the calculated tetragonal structure that, however, is not stable at low temperature. Most importantly, the discontinuity is also observed in the experimental absorption spectrum of the orthorhombic single crystal at low temperature (4 K). However, in contrast to the single crystal, in a polycrystalline perovskite film at 5 K the "gap" is filled by a monotonously increasing absorption throughout the visible range. This feature of thin films points to the potential significance of defect absorption for the excellent light harvesting properties of perovskite-based solar cells. PMID:26278260

  9. Measurement of radical-species concentrations and polycyclic aromatic hydrocarbons in flames by fluorescence and absorption using a tunable dye laser. Progress report, March 1, 1980-February 28, 1981

    SciTech Connect

    Lucht, R.P.; Sweeney, D.W.; Laurendeau, N.M.

    1981-03-01

    A theoretical and experimental investigation of OH saturated fluorescence is described. The goal of the research is to develop a saturated fluorescence technique which will yield accurate molecular number densities over a wide range of flame pressure, temperature, and composition. Experimentally, OH is excited by a ten nanosecond pulse from a Nd:YAG-pumped dye laser tuned to an isolated rotational transition in the (0,0) band of the A/sup 2/..sigma../sup +/-X/sup 2/ pi electronic system. The resulting fluorescence signal is resolved both spectrally and temporally. Total OH number densities are calculated by collecting fluorescence from the directly excited upper rotational level, and using the balanced cross-rate model to analyze the experimental data. Fluorescence measurements of OH number density agree to within a factor of three with the results of independent OH absorption measurements. Significantly, the ratio of the fluorescence signal to the number density measured by absorption is nearly the same in 30, 100 and 250 torr H/sub 2//O/sub 2//N/sub 2/ flat flames, demonstrating the insensitivity of the saturated fluorescence signal to the quenching environment of the radical. Collisional transfer in excited OH is studied by recording the time development of OH fluorescence spectrum. The experimental spectra are compared with the results of time-dependent computer modeling. By varying rotational transfer rates until the calculated and experimental spectra agree, rotational transfer cross sections can be calculated. The signal processing system was thoroughly checked by comparing the photomultiplier output to that of a fast photodiode, and by comparing single pulse Rayleigh scattering and fluorescence traces with sampling oscilloscope traces.

  10. Determination of mercury distribution inside spent compact fluorescent lamps by atomic absorption spectrometry

    SciTech Connect

    Rey-Raap, Natalia

    2012-05-15

    Highlights: Black-Right-Pointing-Pointer New treatments for CFL are required considering the aim of Directive 202/96/CE. Black-Right-Pointing-Pointer It is shown that most of the mercury introduced into a CFL is in the phosphor powder. Black-Right-Pointing-Pointer Experimental conditions for microwave-assisted sample digestion followed by AAS measurements are described. Black-Right-Pointing-Pointer By washing the glass it is possible to reduce the concentration below legal limits. - Abstract: In this study, spent compact fluorescent lamps were characterized to determine the distribution of mercury. The procedure used in this research allowed mercury to be extracted in the vapor phase, from the phosphor powder, and the glass matrix. Mercury concentration in the three phases was determined by the method known as cold vapor atomic absorption spectrometry. Median values obtained in the study showed that a compact fluorescent lamp contained 24.52 {+-} 0.4 ppb of mercury in the vapor phase, 204.16 {+-} 8.9 ppb of mercury in the phosphor powder, and 18.74 {+-} 0.5 ppb of mercury in the glass matrix. There are differences in mercury concentration between the lamps since the year of manufacture or the hours of operation affect both mercury content and its distribution. The 85.76% of the mercury introduced into a compact fluorescent lamp becomes a component of the phosphor powder, while more than 13.66% is diffused through the glass matrix. By washing and eliminating all phosphor powder attached to the glass surface it is possible to classified the glass as a non-hazardous waste.

  11. Describing Two-Photon Absorptivity of Fluorescent Proteins with a New Vibronic Coupling Mechanism

    PubMed Central

    Makarov, N. S.; Tillo, S. E.; Hughes, T. E.; Rebane, A.

    2012-01-01

    Fluorescent proteins (FPs) are widely used in two-photon microscopy as genetically-encoded probes. Understanding the physical basics of their two-photon absorption (2PA) properties is therefore crucial for creation of two-photon brighter mutants. On the other hand, it can give us better insight into molecular interactions of the FP chromophore with complex protein environment. It is known that, compared to one-photon absorption spectrum, where the pure electronic transition is the strongest, the 2PA spectrum of a number of FPs is dominated by a vibronic transition. The physical mechanism of such intensity redistribution is not understood. Here we present a new physical model that explains this effect through the “Herzberg-Teller”-type vibronic coupling of the difference between the permanent dipole moments in the ground and excited states (Δμ) to the bond-length-alternating coordinate. This model also enables us to quantitatively describe a large variability of the 2PA peak intensity in a series of red FPs with the same chromophore through the interference between the “Herzberg-Teller” and Franck-Condon terms. PMID:22224830

  12. A step toward standardization: development of accurate measurements of X-ray absorption and fluorescence.

    PubMed

    Chantler, Christopher T; Barnea, Zwi; Tran, Chanh Q; Rae, Nicholas A; de Jonge, Martin D

    2012-11-01

    This paper explains how to take the counting precision available for XAFS (X-ray absorption fine structure) and attenuation measurements, of perhaps one part in 10(6) in special cases, to produce a local variance below 0.01% and an accuracy of attenuation of the order 0.01%, with an XAFS accuracy at a similar level leading to the determination of dynamical bond lengths to an accuracy similar to that obtained by standard and experienced crystallographic measurements. This includes the necessary corrections for the detector response to be linear, including a correction for dark current and air-path energy dependencies; a proper interpretation of the range of sample thicknesses for absorption experiments; developments of methods to measure and correct for harmonic contamination, especially at lower energies without mirrors; the significance of correcting for the actual bandwidth of the beam on target after monochromation, especially for the portability of results and edge structure from one beamline to another; definitions of precision, accuracy and XAFS accuracy suitable for theoretical model analysis; the role of additional and alternative high-accuracy procedures; and discusses some principles regarding data formats for XAFS and for the deposition of data sets with manuscripts or to a database. Increasingly, the insight of X-ray absorption and the standard of accuracy needed requires data with high intrinsic precision and therefore with allowance for a range of small but significant systematic effects. This is always crucial for absolute measurements of absorption, and is of equal importance but traditionally difficult for (usually relative) measurements of fluorescence XAFS or even absorption XAFS. Robust error analysis is crucial so that the significance of conclusions can be tested within the uncertainties of the measurements. Errors should not just include precision uncertainty but should attempt to include estimation of the most significant systematic error

  13. Environmentally friendly Zn0.75Cd0.25S/PVA heterosystem nanocomposite: UV-stimulated emission and absorption spectra

    NASA Astrophysics Data System (ADS)

    Imam, N. G.; Mohamed, Mohamed Bakr

    2016-02-01

    Zn0.75Cd0.25S nanoparticles prepared at different temperatures were composited with polyvinyl alcohol for functionalization it in wide spectrum of applications such as in photocatalysis. The nanostructure of the Zn0.75Cd0.25S mother phase is confirmed by X-ray diffraction in addition to absorption and fluorescence spectra. UV/VIS. measurements show that, the transmittance coefficient of Zn0.75Cd0.25S/PVA nanocomposite is lesser than that of pure PVA by 0.33% and varies upon increasing the preparation temperature; reaching a maximum value for the sample prepared at 300 °C. It was found that the optical band gap tunes with annealing temperature which, in turns, with particle size. The refractive index of the Zn0.75Cd0.25S/PVA nanocomposite films decrease with increasing wavelength and saturates at high wavelengths. The optical conductivity increases with increasing photon energy which may be due to the excitation of electrons by photon energy. The optical conductivity of Zn0.75Cd0.25S/PVA nanocomposite is lesser than that of pure PVA and it decreases as the preparation temperature of Zn0.75Cd0.25S nanoparticles in PVA matrix increases which could be related to the decrease in the extinction coefficient and the density of localized states in the gap. Abroad peak deconvoluted, by Gaussian fitting function, into two violet and blue colors was observed in the fluorescence spectra under UV light irradiation. The two emission bands are attributed to band edge emission and neutral oxygen vacancies respectively. Analysis of fluorescence (FL) spectra reveals quenching in FL intensity and a peak shifting towards the lower wavelength side with increasing the preparation temperature of the mother phase. The results suggest that the 200 °C Zn0.75Cd0.25S/PVA nanocomposites have been regarded as a promising candidate in many technical fields, such as photocatalytic hydrogen production and/or photocatalytic degradation of organic dyes under UV irradiation due to its high optical

  14. Diagnostics of a see-through hollow cathode discharge by emission, absorption, and fluorescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Taylor, Nicholas

    Atomic line filters have been suggested to be attractive in areas of Doppler velocimetry, resonance fluorescence detection, and resonance ionization detection. They are based on the resonant absorption of photons by an atomic vapor, and allow all other radiation to pass. This allows the detection of very low levels of light superimposed on a large optical background. Several elements have been studied for use as atomic line filters, such as the alkali metals, alkaline earths, and thallium. As previously recognized, thallium is especially attractive since the 535.046 nm metastable transition overlaps with the second harmonic output of an Nd:La2Be2O 5 (BEL) laser (1070 nm). This makes thallium ideal for certain applications as an atomic line filter. Recently a see-through hollow cathode lamp, or galvatron (Hamamatsu), was made commercially available. The galvatron geometry is unique compared to traditional hollow cathode lamps since the cathode and cell are oriented in a T-shape, with the cathode bored completely through to allow the propagation of a light source through the cathode. This allows multi-step excitation of the atomic vapor, not easily accomplished with a traditional hollow cathode lamp. The advantages that a galvatron offers over conventional atomic reservoirs make it an attractive candidate for the application as an atomic line filter; however, little spectroscopic data have been found in the literature. For this reason, Doppler temperatures, number densities, quantum efficiencies, and lifetimes have been determined in order to characterize this atomic reservoir as a potential atomic line filter. These parameters are determined by use of various spectroscopic techniques which include emission, absorption, time-resolved fluorescence, and time-resolved laser-induced saturated fluorescence spectroscopy. From these measurements, it has been demonstrated that a galvatron is an attractive atomic reservoir for applications as an atomic line filter. The

  15. Absorption spectra of AgI at pressures to 136 kbar

    SciTech Connect

    Liebenberg, D.H.; Hudson, J.

    1981-01-01

    Spectral absorption measurements in AgI are reported at pressures up to 136 kbar using a diamond anvil cell. In the NaCl phase between 5 and 70 kbar the absorption edge shift is found to be nearly linear with pressure. No indication of a sudden jump into a CsCl phase is found near 100 kbar and the possible influence of larger pressure gradients in earlier measurements is discussed.

  16. The effects of pH and surfactants on the absorption and fluorescence properties of ochratoxin A and zearalenone.

    PubMed

    Li, Taihua; Kim, Bo Bae; Ha, Tae Hwan; Shin, Yong-Beom; Kim, Min-Gon

    2015-11-01

    The pH and surfactant dependencies of the absorption and fluorescence properties of ochratoxin A (OTA) and zearalenone (ZEN), the main mycotoxins found as contaminants in foods and feeds, were evaluated. Three surfactants with different ionic properties were investigated, namely sodium dodecyl sulfate (SDS, anionic), Tween 20 (nonionic) and hexadecyltrimethylammonium bromide (CTAB, cationic). The results show that the effects of pH on the absorption wavelength maxima and fluorescence efficiencies of the mycotoxins, which are a consequence of the presence of acidic phenol and/or carboxyl containing fluorophores, are dependent on the ionic nature of the added surfactants. Specifically, the fluorescence responses to pH changes of OTA and ZEN are similar in the presence or absence of Tween 20 and SDS. By contrast, the pH-dependent fluorescence properties of these mycotoxins are altered when CTAB is present in the solutions. Moreover, unlike OTA, ZEN in aqueous solution displays almost no fluorescence. However, fluorescence enhancement takes place when surfactants are present in aqueous solutions of this mycotoxin. The results of this study demonstrate that the different microenvironments, present in the organized micellar systems created by the individual surfactants, can be potentially employed to modulate the sensitivities and selectivities of the fluorescence detection of OTA or ZEN.

  17. Using violet laser-induced chlorophyll fluorescence emission spectra for crop yield assessment of cowpea (Vigna unguiculata (L) Walp) varieties

    NASA Astrophysics Data System (ADS)

    Anderson, Benjamin; Buah-Bassuah, Paul K.; Tetteh, Jonathan P.

    2004-07-01

    The use of violet laser-induced chlorophyll fluorescence (LICF) emission spectra to monitor the growth of five varieties of cowpea in the University of Cape Coast Botanical Garden is presented. Radiation from a continuous-wave violet laser diode emitting at 396 nm through a fibre is closely incident on in vivo leaves of cowpea to excite chlorophyll fluorescence, which is detected by an integrated spectrometer with CCD readout. The chlorophyll fluorescence spectra with peaks at 683 and 731 nm were used for growth monitoring of the cowpea plants over three weeks and analysed using Gaussian spectral functions with curve fitted parameters to determine the peak positions, area under the spectral curve and the intensity ratio F683/F731. The variation in the intensity ratio of the chlorophyll bands showed sensitive changes indicating the photosynthetic activity of the cowpea varieties. A discussion of the fluorescence result as compared to conventional assessment is presented with regard to discrimination between the cowpea varieties in terms of crop yield performance.

  18. Sticking to (first) principles: quantum molecular dynamics and Bayesian probabilistic methods to simulate aquatic pollutant absorption spectra.

    PubMed

    Trerayapiwat, Kasidet; Ricke, Nathan; Cohen, Peter; Poblete, Alex; Rudel, Holly; Eustis, Soren N

    2016-08-10

    This work explores the relationship between theoretically predicted excitation energies and experimental molar absorption spectra as they pertain to environmental aquatic photochemistry. An overview of pertinent Quantum Chemical descriptions of sunlight-driven electronic transitions in organic pollutants is presented. Second, a combined molecular dynamics (MD), time-dependent density functional theory (TD-DFT) analysis of the ultraviolet to visible (UV-Vis) absorption spectra of six model organic compounds is presented alongside accurate experimental data. The functional relationship between the experimentally observed molar absorption spectrum and the discrete quantum transitions is examined. A rigorous comparison of the accuracy of the theoretical transition energies (ΔES0→Sn) and oscillator strength (fS0→Sn) is afforded by the probabilistic convolution and deconvolution procedure described. This method of deconvolution of experimental spectra using a Gaussian Mixture Model combined with Bayesian Information Criteria (BIC) to determine the mean (μ) and standard deviation (σ) as well as the number of observed singlet to singlet transition energy state distributions. This procedure allows a direct comparison of the one-electron (quantum) transitions that are the result of quantum chemical calculations and the ensemble of non-adiabatic quantum states that produce the macroscopic effect of a molar absorption spectrum. Poor agreement between the vertical excitation energies produced from TD-DFT calculations with five different functionals (CAM-B3LYP, PBE0, M06-2X, BP86, and LC-BLYP) suggest a failure of the theory to capture the low energy, environmentally important, electronic transitions in our model organic pollutants. However, the method of explicit-solvation of the organic solute using the quantum Effective Fragment Potential (EFP) in a density functional molecular dynamics trajectory simulation shows promise as a robust model of the hydrated organic

  19. Intrinsic fluorescence spectra characteristics of vitamin B1, B2, and B6

    NASA Astrophysics Data System (ADS)

    Yang, Hui; Xiao, Xue; Zhao, Xuesong; Hu, Lan; Lv, Caofang; Yin, Zhangkun

    2015-11-01

    This paper presents the intrinsic fluorescence characteristics of vitamin B1, B2 and B6 measured with 3D fluorescence Spectrophotometer. Three strong fluorescence areas of vitamin B2 locate at λex/λem=270/525nm, 370/525nm and 450/525nm, one fluorescence areas of vitamin B1 locates at λex/λem=370/460nm, two fluorescence areas of vitamin B6 locates at λex/λem=250/370nm and 325/370nm were found. The influence of pH of solution to the fluorescence profile was also discussed. Using the PARAFAC algorithm, 10 vitamin B1, B2 and B6 mixed solutions were successfully decomposed, and the emission profiles, excitation profiles, central wavelengths and the concentration of the three components were retrieved precisely through about 5 iteration times.

  20. Two-Dimensional Potentials of Mean Force of Nile Red in Intact and Damaged Model Bilayers. Application to Calculations of Fluorescence Spectra.

    PubMed

    Singh, Gurpreet; Chamberlin, Adam C; Zhekova, Hristina R; Noskov, Sergei Y; Tieleman, D Peter

    2016-01-12

    Fluorescent dyes revolutionized and expanded our understanding of biological membranes. The interpretation of experimental fluorescence data in terms of membrane structure, however, requires detailed information about the molecular environment of the dyes. Nile red is a fluorescent molecule whose excitation and emission maxima depend on the polarity of the solvent. It is mainly used as a probe to study lipid microenvironments, for example in imaging the progression of damage to the myelin sheath in multiple sclerosis. In this study, we determine the position and orientation of Nile red in lipid bilayers by calculating two-dimensional Potential of Mean Force (2D-PMF) profiles in a defect-free 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) bilayer and in damaged bilayers containing two mixtures of the oxidized lipid 1-palmitoyl-2-(9'-oxo-nonanoyl)-sn-glycero-3-phosphocholine and POPC. From 2D-PMF simulations we obtain positions and orientations of Nile Red corresponding to the minimum on the binding free energy surface in three different membrane environments with increasing amounts of water, mimicking damage in biological tissue. Using representative snapshots from the simulations, we use combined quantum mechanical/molecular mechanical (QM/MM) models to calculate the emission spectrum of Nile red as a function of its local solvation environment. The results of QM and QM/MM computations are in qualitative agreement with the experimentally observed shift in fluorescence for the dye moving from aqueous solution to the more hydrophobic environment of the lipid interiors. The range of the conformation dependent values of the computed absorption-emission spectra and the lack of solvent relaxation effects in the QM/MM calculations made it challenging to delineate specific differences between the intact and damaged bilayers.

  1. Theoretical UV absorption spectra of hydrodynamically escaping O{sub 2}/CO{sub 2}-rich exoplanetary atmospheres

    SciTech Connect

    Gronoff, G.; Mertens, C. J.; Norman, R. B.; Maggiolo, R.; Wedlund, C. Simon; Bell, J.; Bernard, D.; Parkinson, C. J.; Vidal-Madjar, A.

    2014-06-20

    Characterizing Earth- and Venus-like exoplanets' atmospheres to determine if they are habitable and how they are evolving (e.g., equilibrium or strong erosion) is a challenge. For that endeavor, a key element is the retrieval of the exospheric temperature, which is a marker of some of the processes occurring in the lower layers and controls a large part of the atmospheric escape. We describe a method to determine the exospheric temperature of an O{sub 2}- and/or CO{sub 2}-rich transiting exoplanet, and we simulate the respective spectra of such a planet in hydrostatic equilibrium and hydrodynamic escape. The observation of hydrodynamically escaping atmospheres in young planets may help constrain and improve our understanding of the evolution of the solar system's terrestrial planets' atmospheres. We use the dependency of the absorption spectra of the O{sub 2} and CO{sub 2} molecules on the temperature to estimate the temperature independently of the total absorption of the planet. Combining two observables (two parts of the UV spectra that have a different temperature dependency) with the model, we are able to determine the thermospheric density profile and temperature. If the slope of the density profile is inconsistent with the temperature, then we infer the hydrodynamic escape. We address the question of the possible biases in the application of the method to future observations, and we show that the flare activity should be cautiously monitored to avoid large biases.

  2. SYNCHROTRON POLARIZATION AND SYNCHROTRON SELF-ABSORPTION SPECTRA FOR A POWER-LAW PARTICLE DISTRIBUTION WITH FINITE ENERGY RANGE

    SciTech Connect

    Fouka, M.; Ouichaoui, S. E-mail: souichaoui@usthb.dz

    2011-12-10

    We have derived asymptotic forms for the degree of polarization of the optically thin synchrotron and for synchrotron self-absorption (SSA) spectra assuming a power-law particle distribution of the form N({gamma}) {approx} {gamma}{sup -p} with {gamma}{sub 1} < {gamma} < {gamma}{sub 2}, especially for a finite high-energy limit, {gamma}{sub 2}, in the case of an arbitrary pitch angle. The new results inferred concern more especially the high-frequency range x >> {eta}{sup 2} with parameter {eta} = {gamma}{sub 2}/{gamma}{sub 1}. The calculated SSA spectra concern instantaneous photon emission where cooling effects are not considered. They have been obtained by also ignoring likely effects such as Comptonization, pair creation and annihilation, as well as magnetic photon splitting. To that aim, in addition to the two usual absorption frequencies, a third possible one has been derived and expressed in terms of the Lambert W function based on the analytical asymptotic form of the absorption coefficient, {alpha}{sub {nu}}, for the high-frequency range {nu} >> {nu}{sub 2} (with {nu}{sub 2} the synchrotron frequency corresponding to {gamma}{sub 2}). We have shown that the latter frequency may not have realistic applications in astrophysics, except in the case of an adequate set of parameters allowing one to neglect Comptonization effects. More detailed calculations and discussions are presented.

  3. a Theoretical Model for Wide-Band Infrared-Absorption Molecular Spectra at any Pressure: Fiction or Reality?

    NASA Astrophysics Data System (ADS)

    Buldyreva, Jeanna; Vander Auwera, Jean

    2014-06-01

    Various atmospheric applications require modeling of infrared absorption by the main atmospheric species in wide ranges of frequencies, pressures and temperatures. For different pressure regimes, different mechanisms are responsible for the observed intensities of vibration-rotation line manifolds, and the structure of the bands changes drastically when going from low to high densities. Therefore, no universal theoretical model exists presently to interpret simultaneously collapsed band-shapes observed at very high pressures and isolated-line shapes recorded in sub-atmospheric regimes. Using CO_2 absorption spectra as an example, we introduce some improvements in the non-Markovian Energy-Corrected Sudden model, developed for high-density spectra of arbitrary tensorial rank and generalized recently to parallel and perpendicular infrared absorption bands, and test the applicability of this approach for the case of nearly Doppler pressure regime via comparisons with recently recorded experimental intensities. J.V. Buldyreva and L. Bonamy, Phys. Rev. A 60(1), 370-376 (1999). J. Buldyreva and L. Daneshvar, J. Chem. Phys. 139, 164107 (2013). L. Daneshvar, T. Földes, J. Buldyreva, J. Vander Auwera, J. Quant. Spectrosc. Radiat. Transfer 2014 (to be submitted).

  4. Photonic reagents for concentration measurement of flu-orescent proteins with overlapping spectra

    NASA Astrophysics Data System (ADS)

    Goun, Alexei; Bondar, Denys I.; Er, Ali O.; Quine, Zachary; Rabitz, Herschel A.

    2016-05-01

    By exploiting photonic reagents (i.e., coherent control by shaped laser pulses), we employ Optimal Dynamic Discrimination (ODD) as a novel means for quantitatively characterizing mixtures of fluorescent proteins with a large spectral overlap. To illustrate ODD, we simultaneously measured concentrations of in vitro mixtures of Enhanced Blue Fluorescent Protein (EBFP) and Enhanced Cyan Fluorescent Protein (ECFP). Building on this foundational study, the ultimate goal is to exploit the capabilities of ODD for parallel monitoring of genetic and protein circuits by suppressing the spectral cross-talk among multiple fluorescent reporters.

  5. Photonic reagents for concentration measurement of flu-orescent proteins with overlapping spectra

    PubMed Central

    Goun, Alexei; Bondar, Denys I.; Er, Ali O.; Quine, Zachary; Rabitz, Herschel A.

    2016-01-01

    By exploiting photonic reagents (i.e., coherent control by shaped laser pulses), we employ Optimal Dynamic Discrimination (ODD) as a novel means for quantitatively characterizing mixtures of fluorescent proteins with a large spectral overlap. To illustrate ODD, we simultaneously measured concentrations of in vitro mixtures of Enhanced Blue Fluorescent Protein (EBFP) and Enhanced Cyan Fluorescent Protein (ECFP). Building on this foundational study, the ultimate goal is to exploit the capabilities of ODD for parallel monitoring of genetic and protein circuits by suppressing the spectral cross-talk among multiple fluorescent reporters. PMID:27181496

  6. Investigation of the electronic absorption spectra and the circular dichroism spectra of binuclear tetra-. mu. -mandelato complexes of Mo/sub 2//sup 4 +/

    SciTech Connect

    Golovaneva, I.F.; Akhmedov, E.L.; Kotel'nikova, A.S.

    1987-05-01

    The IR, electronic absorption, and circular dichroism spectra of the binuclear tetra-..mu..-mandelates of molybdenum(II) (Mo/sub 2//D-(-)-OOCCH(OH)C/sub 6/H/sub 5///sub 4/) and (Mo/sub 2//L-(+)-OOCCH(OH)C/sub 6/H/sub 5///sub 4/) have been studied. It has been established that Cotton effects are induced in all the electronic transitions of the symmetric (Mo/sub 2/O/sub 8/)chromophore under the influence of the asymmetric atom of the optically active mandelato ligand. The observed electronic transitions have been assigned on the basis of an analysis of the spectroscopic data obtained.

  7. Sizeable red-shift of absorption and fluorescence of subporphyrazine induced by peripheral push and pull substitution.

    PubMed

    Liang, Xu; Shimizu, Soji; Kobayashi, Nagao

    2014-11-18

    Peripheral substitution with electron-donating (push) and electron-withdrawing (pull) substituents caused a sizeable red-shift of the Q band absorption and fluorescence of subporphyrazine, and the red-shift was controlled by the push substituents. Control of the chromophore symmetry and inherent molecular chirality arising from the pattern of substitution were also investigated.

  8. Extraction of pigment information from near-UV vis absorption spectra of extra virgin olive oils.

    PubMed

    Domenici, Valentina; Ancora, Donatella; Cifelli, Mario; Serani, Andrea; Veracini, Carlo Alberto; Zandomeneghi, Maurizio

    2014-09-24

    This work reports a new approach to extract the maximum chemical information from the absorption spectrum of extra virgin olive oils (EVOOs) in the 390-720 nm spectral range, where "oil pigments" dominate the light absorption. Four most important pigments, i.e., two carotenoids (lutein and β-carotene) and two chlorophylls (pheophytin-a and pheophytin-b), are chosen as reference oil pigments, being present in all the reported analytical data regarding pigments of EVOOs. The method allows the quantification of the concentration values of these four pigments directly from the deconvolution of the measured absorption spectrum of EVOOs. Advantages and limits of the method and the reliability of the pigment family quantification are discussed. The main point of this work is the description of a fast and simple method to extract of such information in less than a minute, through the mathematical analysis of the UV-vis spectrum of untreated samples of oil.

  9. Disentangling vibronic and solvent broadening effects in the absorption spectra of coumarin derivatives for dye sensitized solar cells.

    PubMed

    Cerezo, Javier; Avila Ferrer, Francisco J; Santoro, Fabrizio

    2015-05-01

    We simulate from first-principles the absorption spectra of five structure-related coumarin derivatives utilized in dye sensitized solar cells (DSSCs), investigating the vibronic and solvent contributions to the position and width of the spectra in ethanol. Ground and excited state potential energy surfaces (PESs) are modeled by Density Functional Theory (DFT) and its time-dependent (TD) expression for the excited state (TD-DFT). The solute vibronic structure associated with the spectrum is calculated by a TD formalism, accounting for both Duschinsky and temperature effects, while solvent inhomogeneous broadening is evaluated according to Marcus' theory, computing the solvent reorganization energy by the state-specific implementation of the polarizable continuum model (PCM) within TD-DFT. We adopted both the standard hybrid PBE0 and the range separated CAM-B3LYP functionals showing that the latter performs better both concerning the vibronic and solvent-induced contributions to the absorption lineshape. The different predictions of the two functionals are then rationalized in terms of the charge transfer (CT) character of the transitions showing that, in this class of compounds, it is strongly dependent on the nuclear structure. Such a dependence introduces a bias in the PBE0 PES that has a drastic impact on the vibronic spectra. We show that both the intrinsic vibronic structure and the solvent broadening play a relevant role in differentiating the absorption width of the five dyes. In this sense, our results provide a guide to understand the sources of spectral broadening of this family of dyes, a valuable help for a rational design of new molecules to improve DSSC devices.

  10. All-electron first-principles GW+Bethe-Salpeter calculation for optical absorption spectra of sodium clusters

    SciTech Connect

    Noguchi, Yoshifumi; Ohno, Kaoru

    2010-04-15

    The optical absorption spectra of sodium clusters (Na{sub 2n}, n{<=} 4) are calculated by using an all-electron first-principles GW+Bethe-Salpeter method with the mixed-basis approach within the Tamm-Dancoff approximation. In these small systems, the excitonic effect strongly affects the optical properties due to the confinement of exciton in the small system size. The present state-of-the-art method treats the electron-hole two-particle Green's function by incorporating the ladder diagrams up to the infinite order and therefore takes into account the excitonic effect in a good approximation. We check the accuracy of the present method by comparing the resulting spectra with experiments. In addition, the effect of delocalization in particular in the lowest unoccupied molecular orbital in the GW quasiparticle wave function is also discussed by rediagonalizing the Dyson equation.

  11. The effect of pathological processes on absorption and scattering spectra of samples of bile and pancreatic juice

    NASA Astrophysics Data System (ADS)

    Giraev, K. M.; Ashurbekov, N. A.; Magomedov, M. A.; Murtazaeva, A. A.; Medzhidov, R. T.

    2015-07-01

    Spectra of optical transmission coefficients and optical reflectance for bile and pancreatic juice samples were measured experimentally for different forms of pathologies of the pancreas within the range of 250-2500 nm. The absorption and scattering spectra, as well as the spectrum of the anisotropy factor of scattering, were determined based on the results obtained using the reverse Monte Carlo method. The surface morphology for the corresponding samples of the biological media was studied employing electron microscopy. The dynamics of the optical properties of the biological media was determined depending on the stage of the pathology. It has been demonstrated that the results of the study presented are in a good agreement with pathophysiological data and could supplement and broaden the results of conventional methods for diagnostics of the pancreas.

  12. Absorption spectra of two-level atoms interacting with a strong polychromatic pump field and an arbitrarily intense probe field

    NASA Astrophysics Data System (ADS)

    Yoon, Tai Hyun; Chung, Myung Sai; Lee, Hai-Woong

    1999-09-01

    A numerical method is introduced that solves the optical Bloch equations describing a two-level atom interacting with a strong polychromatic pump field with an equidistant spectrum and an arbitrarily intense monochromatic probe field. The method involves a transformation of the optical Bloch equations into a system of equations with time-independent coefficients at steady state via double harmonic expansion of the density-matrix elements, which is then solved by the method of matrix inversion. The solutions so obtained lead immediately to the determination of the polarization of the atomic medium and of the absorption and dispersion spectra. The method is applied to the case when the pump field is bichromatic and trichromatic, and the physical interpretation of the numerically computed spectra is given.

  13. A benzo-15-crown-5-modifying ratiometric-absorption and fluorescent OFF-ON chemosensor for Cu2 +

    NASA Astrophysics Data System (ADS)

    Chen, Yuting; Wang, Xinxin; Wang, Kaili; Zhang, Xiuling

    2016-05-01

    One new benzo-15-crown-5-modifying fluorene Schiff base (FBC), together with the Cdbnd N-linked fluorene-3,4-dimethoxybenzene (FBDMO) and fluorene-benzene (FB) references, has been designed and facilely synthesized. The binding of Cu2 + with nitrogen atom of Cdbnd N moiety in these three compounds can inhibit the photo-induced electronic transition process and induce the ratiometric-absorption and fluorescent OFF-ON response to Cu2 +. Whereas the employment of benzo-15-crown-5 moiety in FBC as additional binding platform for Cu2 + not only amplifies the fluorescent enhancement of FBCvia preventing the isomerization of Cdbnd N moiety, but also endows this compound high selectivity and rapid response towards Cu2 + over the references FB and FBDMO. These results render FBC highly sensitive ratiometric-absorption and fluorescent OFF-ON detecting potential for Cu2 + with the detection limit of 3.91 × 10- 6 M.

  14. Upper limits for stratospheric H2O2 and HOCl from high resolution balloon-borne infrared solar absorption spectra

    NASA Technical Reports Server (NTRS)

    Larsen, J. C.; Rinsland, C. P.; Goldman, A.; Murcray, D. G.; Murcray, F. J.

    1985-01-01

    Solar absorption spectra from two stratospheric balloon flights have been analyzed for the presence of H2O2 and HOCl absorption in the 1230.0 to 1255.0 per cm region. The data were recorded at 0.02 per cm resolution during sunset with the University of Denver interferometer system on October 27, 1978 and March 23, 1981. Selected spectral regions were analyzed with the technique of nonlinear least squares spectral curve fitting. Upper limits of 0.33 ppbv for H2O2 and 0.36 ppbv for HOCl near 28 km are derived from the 1978 flight data while upper limits of 0.44 ppbv for H2O2 and 0.43 ppbv for HOCl at 29.5 km are obtained from the 1981 flight data.

  15. First detection of ionized helium absorption lines in infrared K band spectra of O-type stars

    NASA Technical Reports Server (NTRS)

    Conti, Peter S.; Block, David L.; Geballe, T. R.; Hanson, Margaret M.

    1993-01-01

    We have obtained high SNR, moderate-resolution K band spectra of two early O-type main sequence stars, HD 46150 O5 V, and HD 46223 O4 V, in the Rosette Nebula. We report the detection, for the first time, of the 2.189 micron He II line in O-type stars. Also detected is the 2.1661 micron Br-gamma line in absorption. The 2.058 micron He I line appears to be present in absorption in both stars, although its appearance at our resolution is complicated by atmospheric features. These three lines can form the basis for a spectral classification system for hot stars in the K band that may be used at infrared wavelengths to elucidate the nature of those luminous stars in otherwise obscured H II and giant H II regions.

  16. Final State Projection Method in Charge-Transfer Multiplet Calculations: An analysis of Ti L-edge Absorption Spectra

    PubMed Central

    Kroll, Thomas; Solomon, Edward I.; de Groot, Frank M. F.

    2016-01-01

    A projection method to determine the final state configuration character of all peaks in a charge transfer multiplet calculation of a 2p X-ray absorption spectrum is presented using a d0 system as an example. The projection method is used to identify the most important influences on spectral shape and to map out the configuration weights. The spectral shape of a 2p X-ray absorption or L2,3-edge spectrum is largely determined by the ratio of the 2p core-hole interactions relative to the 2p3d atomic multiplet interaction. This leads to a non-trivial spectral assignment, which makes a detailed theoretical description of experimental spectra valuable for the analysis of bonding. PMID:26226507

  17. Final-State Projection Method in Charge-Transfer Multiplet Calculations: An Analysis of Ti L-Edge Absorption Spectra.

    PubMed

    Kroll, Thomas; Solomon, Edward I; de Groot, Frank M F

    2015-10-29

    A projection method to determine the final-state configuration character of all peaks in a charge transfer multiplet calculation of a 2p X-ray absorption spectrum is presented using a d(0) system as an example. The projection method is used to identify the most important influences on spectral shape and to map out the configuration weights. The spectral shape of a 2p X-ray absorption or L2,3-edge spectrum is largely determined by the ratio of the 2p core-hole interactions relative to the 2p3d atomic multiplet interaction. This leads to a nontrivial spectral assignment, which makes a detailed theoretical description of experimental spectra valuable for the analysis of bonding. PMID:26226507

  18. In vivo fluorescence spectra unmixing and autofluorescence removal by sparse nonnegative matrix factorization.

    PubMed

    Montcuquet, Anne-Sophie; Hervé, Lionel; Navarro, Fabrice; Dinten, Jean-Marc; Mars, Jérôme I

    2011-09-01

    Fluorescence imaging locates fluorescent markers that specifically bind to targets; like tumors, markers are injected to a patient, optimally excited with near-infrared light, and located thanks to backward-emitted fluorescence analysis. To investigate thick and diffusive media, as the fluorescence signal decreases exponentially with the light travel distance, the autofluorescence of biological tissues comes to be a limiting factor. To remove autofluorescence and isolate specific fluorescence, a spectroscopic approach, based on nonnegative matrix factorization (NMF), is explored. To improve results on spatially sparse markers detection, we suggest a new constrained NMF algorithm that takes sparsity constraints into account. A comparative study between both algorithms is proposed on simulated and in vivo data.

  19. Absorption spectra and optical parameters of lithium-potassium sulphate single crystals

    NASA Astrophysics Data System (ADS)

    El-Fadl, A. Abu; Gaffar, M. A.; Omar, M. H.

    1999-09-01

    The optical transmittance and reflectance near the fundamental absorption region along the c- and a-axes of lithium potassium sulphate single crystal (LKS) are measured at room temperature. From the data the absorption coefficient ( α) and the optical band gap ( Eopt.g) were deduced. The type of transition was determined. The steepness parameter ( σ), the temperature dependence of the energy gap and the exciton energy ( E0) were also calculated. The extinction coefficient, the refractive index and both the real and imaginary parts of the dielectric permittivity were calculated as functions of the photon energy.

  20. Dynamics of intramolecular electron transfer reaction of FAD studied by magnetic field effects on transient absorption spectra.

    PubMed

    Murakami, Masaaki; Maeda, Kiminori; Arai, Tatsuo

    2005-07-01

    The kinetics of intermediates generated from intramolecular electron-transfer reaction by photo irradiation of the flavin adenine dinucleotide (FAD) molecule was studied by a magnetic field effect (MFE) on transient absorption (TA) spectra. Existence time of MFE and MFE action spectra have a strong dependence on the pH of solutions. The MFE action spectra have indicated the existence of interconversion between the radical pair and the cation form of the triplet excited state of flavin part. All rate constants of the triplet and the radical pair were determined by analysis of the MFE action spectra and decay kinetics of TA. The obtained values for the interconversion indicate that the formation of cation radical promotes the back electron-transfer reaction to the triplet excited state. Further, rate constants of spin relaxation and recombination have been studied by the time profiles of MFE at various pH. The drastic change of those two factors has been obtained and can be explained by SOC (spin-orbit coupling) induced back electron-transfer promoted by the formation of a stacking conformation at pH > 2.5.

  1. Restricted active space calculations of L-edge X-ray absorption spectra: from molecular orbitals to multiplet states.

    PubMed

    Pinjari, Rahul V; Delcey, Mickaël G; Guo, Meiyuan; Odelius, Michael; Lundberg, Marcus

    2014-09-28

    The metal L-edge (2p → 3d) X-ray absorption spectra are affected by a number of different interactions: electron-electron repulsion, spin-orbit coupling, and charge transfer between metal and ligands, which makes the simulation of spectra challenging. The core restricted active space (RAS) method is an accurate and flexible approach that can be used to calculate X-ray spectra of a wide range of medium-sized systems without any symmetry constraints. Here, the applicability of the method is tested in detail by simulating three ferric (3d(5)) model systems with well-known electronic structure, viz., atomic Fe(3+), high-spin [FeCl6](3-) with ligand donor bonding, and low-spin [Fe(CN)6](3-) that also has metal backbonding. For these systems, the performance of the core RAS method, which does not require any system-dependent parameters, is comparable to that of the commonly used semi-empirical charge-transfer multiplet model. It handles orbitally degenerate ground states, accurately describes metal-ligand interactions, and includes both single and multiple excitations. The results are sensitive to the choice of orbitals in the active space and this sensitivity can be used to assign spectral features. A method has also been developed to analyze the calculated X-ray spectra using a chemically intuitive molecular orbital picture.

  2. Cost and sensitivity of restricted active-space calculations of metal L-edge X-ray absorption spectra.

    PubMed

    Pinjari, Rahul V; Delcey, Mickaël G; Guo, Meiyuan; Odelius, Michael; Lundberg, Marcus

    2016-02-15

    The restricted active-space (RAS) approach can accurately simulate metal L-edge X-ray absorption spectra of first-row transition metal complexes without the use of any fitting parameters. These characteristics provide a unique capability to identify unknown chemical species and to analyze their electronic structure. To find the best balance between cost and accuracy, the sensitivity of the simulated spectra with respect to the method variables has been tested for two models, [FeCl6 ](3-) and [Fe(CN)6 ](3-) . For these systems, the reference calculations give deviations, when compared with experiment, of ≤1 eV in peak positions, ≤30% for the relative intensity of major peaks, and ≤50% for minor peaks. When compared with these deviations, the simulated spectra are sensitive to the number of final states, the inclusion of dynamical correlation, and the ionization potential electron affinity shift, in addition to the selection of the active space. The spectra are less sensitive to the quality of the basis set and even a double-ζ basis gives reasonable results. The inclusion of dynamical correlation through second-order perturbation theory can be done efficiently using the state-specific formalism without correlating the core orbitals. Although these observations are not directly transferable to other systems, they can, together with a cost analysis, aid in the design of RAS models and help to extend the use of this powerful approach to a wider range of transition metal systems.

  3. The Fundamental Quadrupole Band of (14)N2: Line Positions from High-Resolution Stratospheric Solar Absorption Spectra

    NASA Technical Reports Server (NTRS)

    Rinsland, C. P.; Zander, R.; Goldman, A.; Murcray, F. J.; Murcray, D. G.; Grunson, M. R.; Farmer, C. B.

    1991-01-01

    The purpose of this note is to report accurate measurements of the positions of O- and S-branch lines of the (1-0) vibration-rotation quadrupole band of molecular nitrogen ((14)N2) and improved Dunham coefficients derived from a simultaneous least-squares analysis of these measurements and selected infrared and far infrared data taken from the literature. The new measurements have been derived from stratospheric solar occultation spectra recorded with Fourier transform spectrometer (FTS) instruments operated at unapodized spectral resolutions of 0.002 and 0.01 /cm. The motivation for the present investigation is the need for improved N2 line parameters for use in IR atmospheric remote sensing investigations. The S branch of the N2 (1-0) quadrupole band is ideal for calibrating the line-of-sight airmasses of atmospheric spectra since the strongest lines are well placed in an atmospheric window, their absorption is relatively insensitive to temperature and is moderately strong (typical line center depths of 10 to 50% in high-resolution ground-based solar spectra and in lower stratospheric solar occultation spectra), and the volume mixing ratio of nitrogen is constant in the atmosphere and well known. However, a recent investigation has'shown the need to improve the accuracies of the N2 fine positions, intensities, air-broadened half-widths, and their temperature dependences to fully exploit this calibration capability (1). The present investigation addresses the problem of improving the accuracy of the N2 line positions.

  4. X-ray absorption spectra of water within a plane-wave Car-Parrinello molecular dynamics framework

    NASA Astrophysics Data System (ADS)

    Cavalleri, Matteo; Odelius, Michael; Nilsson, Anders; Pettersson, Lars G. M.

    2004-11-01

    We describe the implementation of a simple technique to simulate core-level spectra within the Car-Parrinello plane-waves molecular dynamics framework. The x-ray absorption (XA) spectra are generated using the transition potential technique with the effect of the core hole included through a specifically developed pseudopotential for the core-excited atom. Despite the lack of 1s core orbitals in the pseudopotential treatment, the required transition moments are accurately calculated without reconstruction of the all-electron orbitals. The method is applied to the oxygen XA spectra of water in its various aggregation states, but it is transferable to any first-row element. The computed spectra are compared favorably with the results from all-electron cluster calculations, as well as with experimental data. The periodicity of the plane-wave technique improves the description of condensed phases. The molecular dynamics simulation enables in principle a proper treatment of thermal effects and dynamical averaging in complex systems.

  5. Automatic phase correction of fourier transform NMR spectra based on the dispersion versus absorption (DISPA) lineshape analysis

    NASA Astrophysics Data System (ADS)

    Sotak, Christopher H.; Dumoulin, Charles L.; Newsham, Mark D.

    A method for automatic phase correction of Fourier transform NMR spectra bused on the dispersion versus absorption (DISPA) lineshape analysis is described. The DISPA display of a single misphased Lorentzian line gives a unit circle which has been rotated about the origin (relative to its "reference circle") by a number of degrees equal to the phase misadjustment. This rotation, Φ, is a combination of the zero- and first-order phase angles at the frequency of the resonance. Calculation of Φ for two or more resonances allows the spectral phasing parameters to be determined and applied to correct the spectrum. This approach has been implemented in both automatic and "semi-automatic" modes.

  6. Electronic properties and absorption spectra of ZnSnP{sub 2} using mBJ potential

    SciTech Connect

    Joshi, Ritu Ahuja, B. L.

    2015-06-24

    We present the energy bands and density of states of ZnSnP{sub 2} using full potential linearized augmented plane wave method with modified Becke Johnson potential. It is found that this compound has a direct band gap of about 2.01 eV at Γ point, which originates from the energy difference between P-3p and Sn-5s states. In addition, we have also calculated absorption spectra in the solar energy range and compared it with that of bulk Si to explore the applicability of ZnSnP{sub 2} in photovoltaic and optoelectronic devices.

  7. Impact of broadened laser line-shape on retrievals of atmospheric species from lidar sounding absorption spectra.

    PubMed

    Chen, Jeffrey R; Numata, Kenji; Wu, Stewart T

    2015-02-01

    We examine the impact of broadened laser line-shape on retrievals of atmospheric species from lidar-sounding absorption spectra. The laser is assumed to be deterministically modulated into a stable, nearly top-hat frequency comb to suppress the stimulated Brillouin scattering, allowing over 10-fold pulse energy increase without adding measurement noise. Our model remains accurate by incorporating the laser line-shape factor into the effective optical depth. Retrieval errors arising from measurement noise and model bias are analyzed parametrically and numerically to provide deeper insight. The stable laser line-shape broadening minimally degrades the column-averaged retrieval, but can significantly degrade the multiple-layer retrievals.

  8. Far-infrared absorption spectra of cobalt(III), rhodium(III), and iridium(III). beta. -diketonates

    SciTech Connect

    Oglezneva, I.M.; Isakova, V.G.; Igumenov, I.K.

    1987-03-01

    The IR absorption spectra of the complexes of Co(II), Rh(III), and Ir(III) with acetylacetone, trifluoroacetylacetone, hexafluoroactylacetone, dipivaloylmethane, and pivaloyltrifluoroacetylacetone in the region from 30 to 700 cm/sup -1/ have been examined for the first time. The frequencies of the intramolecular vibrations associated with in-plane and out-of-plane deformations of the chelate rings and deformations of the radicals in the ligands have been assigned. The frequencies of the predominantly stretching nu(MO) vibrations of the metal-oxygen bonds have been identified. Their variation has been compared with NMR data on the redistribution of the electron density in the chelate rings.

  9. Signatures of a conical intersection in photofragment distributions and absorption spectra: Photodissociation in the Hartley band of ozone

    SciTech Connect

    Picconi, David; Grebenshchikov, Sergy Yu.

    2014-08-21

    Photodissociation of ozone in the near UV is studied quantum mechanically in two excited electronic states coupled at a conical intersection located outside the Franck-Condon zone. The calculations, performed using recent ab initio PESs, provide an accurate description of the photodissociation dynamics across the Hartley/Huggins absorption bands. The observed photofragment distributions are reproduced in the two electronic dissociation channels. The room temperature absorption spectrum, constructed as a Boltzmann average of many absorption spectra of rotationally excited parent ozone, agrees with experiment in terms of widths and intensities of diffuse structures. The exit channel conical intersection contributes to the coherent broadening of the absorption spectrum and directly affects the product vibrational and translational distributions. The photon energy dependences of these distributions are strikingly different for fragments created along the adiabatic and the diabatic paths through the intersection. They can be used to reverse engineer the most probable geometry of the non-adiabatic transition. The angular distributions, quantified in terms of the anisotropy parameter β, are substantially different in the two channels due to a strong anticorrelation between β and the rotational angular momentum of the fragment O{sub 2}.

  10. Using of laser spectroscopy and chemometrics methods for identification of patients with lung cancer, patients with COPD and healthy people from absorption spectra of exhaled air

    NASA Astrophysics Data System (ADS)

    Bukreeva, Ekaterina B.; Bulanova, Anna A.; Kistenev, Yury V.; Kuzmin, Dmitry A.; Nikiforova, Olga Yu.; Ponomarev, Yurii N.; Tuzikov, Sergei A.; Yumov, Evgeny L.

    2014-11-01

    The results of application of the joint use of laser photoacoustic spectroscopy and chemometrics methods in gas analysis of exhaled air of patients with chronic respiratory diseases (chronic obstructive pulmonary disease and lung cancer) are presented. The absorption spectra of exhaled breath of representatives of the target groups and healthy volunteers were measured; the selection by chemometrics methods of the most informative absorption coefficients in scan spectra in terms of the separation investigated nosology was implemented.

  11. Spectra Aerosol Light Scattering and Absorption for Laboratory and Urban Aerosol

    NASA Astrophysics Data System (ADS)

    Gyawali, Madhu S.

    Atmospheric aerosols considerably influence the climate, reduce visibility, and cause problems in human health. Aerosol light absorption and scattering are the important factors in the radiation transfer models. However, these properties are associated with large uncertainties in climate modeling. In addition, atmospheric aerosols widely vary in composition and size; their optical properties are highly wavelength dependent. This work presents the spectral dependence of aerosol light absorption and scattering throughout the ultraviolet to near-infrared regions. Data were collected in Reno, NV from 2008 to 2010. Also presented in this study are the aerosol optical and physical properties during carbonaceous aerosols and radiative effects study (CARES) conducted in Sacramento area during 2010. Measurements were made using photoacoustic instruments (PA), including a novel UV 355 nm PA of our design and manufacture. Comparative analyses are presented for three main categories: (1) aerosols produced by wildfires and traffic emissions, (2) laboratory-generated and wintertime ambient urban aerosols, and (3) urban plume and biogenic emissions. In these categories, key questions regarding the light absorption by secondary organic aerosols (SOA), so-called brown carbon (BrC), and black carbon (BC) will be discussed. An effort is made to model the emission and aging of urban and biomass burning aerosol by applying shell-core calculations. Multispectral PA measurements of aerosols light absorption and scattering coefficients were used to calculate the Angstrom exponent of absorption (AEA) and single scattering albedo (SSA). The AEA and SSA values were analyzed to differentiate the aerosol sources. The California wildfire aerosols exhibited strong wavelength dependence of aerosol light absorption with AEA as lambda -1 for 405 and 870 nm, in contrast to the relatively weak wavelength dependence of traffic emissions aerosols for which AEA varied approximately as lambda-1. By using

  12. Photoacoustic-fluorescence in vitro flow cytometry for quantification of absorption, scattering and fluorescence properties of the cells

    NASA Astrophysics Data System (ADS)

    Nedosekin, D. A.; Sarimollaoglu, M.; Foster, S.; Galanzha, E. I.; Zharov, V. P.

    2013-03-01

    Fluorescence flow cytometry is a well-established analytical tool that provides quantification of multiple biological parameters of cells at molecular levels, including their functional states, morphology, composition, proliferation, and protein expression. However, only the fluorescence and scattering parameters of the cells or labels are available for detection. Cell pigmentation, presence of non-fluorescent dyes or nanoparticles cannot be reliably quantified. Herewith, we present a novel photoacoustic (PA) flow cytometry design for simple integration of absorbance measurements into schematics of conventional in vitro flow cytometers. The integrated system allow simultaneous measurements of light absorbance, scattering and of multicolor fluorescence from single cells in the flow at rates up to 2 m/s. We compared various combinations of excitation laser sources for multicolor detection, including simultaneous excitation of PA and fluorescence using a single 500 kHz pulsed nanosecond laser. Multichannel detection scheme allows simultaneous detection of up to 8 labels, including 4 fluorescent tags and 4 PA colors. In vitro PA-fluorescence flow cytometer was used for studies of nanoparticles uptake and for the analysis of cell line pigmentation, including genetically encoded melanin expression in breast cancer cell line. We demonstrate that this system can be used for direct nanotoxicity studies with simultaneous quantification of nanoparticles content and assessment of cell viability using a conventional fluorescent apoptosis assays.

  13. Nonlinear reconstruction of absorption and fluorescence contrast from measured diffuse transmittance and reflectance of a compressed-breast-simulating phantom

    SciTech Connect

    Ziegler, Ronny; Nielsen, Tim; Koehler, Thomas; Grosenick, Dirk; Steinkellner, Oliver; Hagen, Axel; Macdonald, Rainer; Rinneberg, Herbert

    2009-08-20

    We report on the nonlinear reconstruction of local absorption and fluorescence contrast in tissuelike scattering media from measured time-domain diffuse reflectance and transmittance of laser as well as laser-excited fluorescence radiation. Measurements were taken at selected source-detector offsets using slablike diffusely scattering and fluorescent phantoms containing fluorescent heterogeneities. Such measurements simulate in vivo data that would be obtained employing a scanning, time-domain fluorescence mammograph, where the breast is gently compressed between two parallel glass plates, and source and detector optical fibers scan synchronously at various source-detector offsets, allowing the recording of laser and fluorescence mammograms. The diffusion equations modeling the propagation of the laser and fluorescence radiation were solved in frequency domain by the finite element method simultaneously for several modulation frequencies using Fourier transformation and preprocessed experimental data. To reconstruct the concentration of the fluorescent contrast agent, the Born approximation including higher-order reconstructed photon densities at the excitation wavelength was used. Axial resolution was determined that can be achieved by various detection schemes. We show that remission measurements increase the depth resolution significantly.

  14. Determination of vibration-rotation lines intensities from absorption Fourier spectra

    NASA Technical Reports Server (NTRS)

    Mandin, J. Y.

    1979-01-01

    The method presented allows the line intensities to be calculated from either their equivalent widths, heights, or quantities deduced from spectra obtained by Fourier spectrometry. This method has proven its effectiveness in measuring intensities of 60 lines of the molecule H2O with a precision of 10%. However, this method cannot be applied to isolated lines.

  15. Fluorescence Excitation Spectra of Photo-Fragmented Nitrobenzene Using a Picosecond Laser: Potential Evidence for no Produced by Two Distinct Channels.

    NASA Astrophysics Data System (ADS)

    Lue, Christopher J.; Tanjaroon, Chakree; Johnson, J. Bruce; Reeve, Scott W.; Allen, Susan D.

    2013-06-01

    Upon absorption of a UV photon, nitrobenzene can dissociate into C_6H_5O and NO through two different mechanisms. Evidence for these mechanisms was obtained from velocity map imaging (VMI) studies and theoretical calculations. VMI experiments showed NO produced with two distinct rotational distributions, which the calculations explained as a fast and a slow channel for NO production. We have recorded high resolution fluorescence excitation spectra of the NO resulting from photo-fragmented nitrobenzene using a pulsed picosecond tunable laser (pulse width ≈ 15 ps) by means of a two-color process. In the two-color process, photons of a particular energy dissociated the nitrobenzene while photons of a different energy probed the A^2Σ^+← X^2Π_{(1/2,3/2)} NO band system between 225-260 nm. This laser system allowed us to vary the delay between the photolysis and excitation pulses. At longer delays (>1 ns), we observed an increase in the population of NO, which may be evidence that at least two photolysis channels produce NO. We present the spectra we recorded at various photolysis/probe delays ranging from 0.025 to 1.5 ns. The spectral subtraction method we used to observe the production increase is introduced. Hause, M. L.; Herath, N.; Zhu, R.; Lin, M. C. and Suits, A. G. Nat Chem, Nature Publishing Group, 2011, 3, 932-937

  16. [Investigation of FTIR spectra analysis on carbon dioxide absorption with improved amine solution].

    PubMed

    Yin, Wen-xuan; Liu, Jian-zhou; Gao, Li-ping; Jiang, Jing-liang; Wang, Zhi-hua

    2011-05-01

    Carbon dioxide is a major sort of greenhouse gas as well as important carbon resource. With the developments of industries, emission of carbon dioxide has increased sharply. Hence, controls of carbon dioxide emission and resource transformation have become the hotspot of current study. As a new kind of carbon resource, the fields of CO2 research and application are very extensive. Among those methods, the amine absorption has good qualities of faster absorption rate, higher efficiency and so on, so it has been widely studied. But organic amine have such shortcomings: high consumption of heat energy, strong corrosive and easy oxidated, now pursuer mainly focused on the organic amine modified. The results showed that, when the time the amount of antioxidant 1010 is 0.152, the absorption capacity is 2503.53 mL. the volume of analysis is 982.00 mL, and the absorption rate changes more slowly, by FTIR, Samples of its renewable-OH associating is not apparent that the antioxidant content in 1010, oxidation products of the MEA is acid or less oxidation and antioxidant 1010 product in early to respond fully to form stable non-radical compounds. Therefore, the best dosage of antioxidant 1010 is 0.15%. When the time that the amount of Na2SO3 is 0.15%, the absorption capacity is 2922.88 mL. Analysis of the volume is 723.00 mL, by FTIR, which reveals the oxidation products of the MEA is amide -C=O which in alkaline solution can be transiting into primary amine, and be easy absorbing CO2. Comparing the antioxygenic proerty of antioxidant 1010 with Na2SO3, from the absorption rate, the amount of absorption , Na2SO3's antioxidant properties is superior than antioxidant 1010; by infrared spectral analysis, 1010/20% MEA solution's oxidation products is the acid, Na2SO3/20% MEA solutions, the oxidation product is amide, amide solution is advantaged for absorbing CO2, So Na2SO3's antioxidant properties is superior than antioxidant 1010.

  17. Probing Cu(I) in homogeneous catalysis using high-energy-resolution fluorescence-detected X-ray absorption spectroscopy.

    PubMed

    Walroth, Richard C; Uebler, Jacob W H; Lancaster, Kyle M

    2015-06-18

    Metal-to-ligand charge transfer excitations in Cu(I) X-ray absorption spectra are introduced as spectroscopic handles for the characterization of species in homogeneous catalytic reaction mixtures. Analysis is supported by correlation of a spectral library to calculations and to complementary spectroscopic parameters.

  18. Predicting the Shifts of Absorption Maxima of Azulene Derivatives Using Molecular Modeling and ZINDO CI Calculations of UV-Vis Spectra

    ERIC Educational Resources Information Center

    Patalinghug, Wyona C.; Chang, Maharlika; Solis, Joanne

    2007-01-01

    The deep blue color of azulene is drastically changed by the addition of substituents such as CH[subscript 3], F, or CHO. Computational semiempirical methods using ZINDO CI are used to model azulene and azulene derivatives and to calculate their UV-vis spectra. The calculated spectra are used to show the trends in absorption band shifts upon…

  19. An unidentified absorption in the spectra of C-S stars

    NASA Technical Reports Server (NTRS)

    Rybski, P. M.

    1973-01-01

    An absorption feature in the low-dispersion red spectrograms of carbon Mira variables and C-S stars shown to exhibit strikingly different behavior in these similarly appearing carbon and carbonlike stars. Evidence is presented that in the carbon Miras the feature may be due to unresolved bandheads of the (0,0) system of calcium iodide. In this group of stars the feature exhibits a temperature sensitivity similar to absorptions due to calcium chloride and to the neutral sodium doublet. No identification is suggested for the feature appearing among the C-S stars, though there is evidence against it being composed partially of a zero-volt line of neutral scandium.

  20. Performance Enhancement of Polymer Solar Cells by Using Two Polymer Donors with Complementary Absorption Spectra.

    PubMed

    Lu, Heng; Zhang, Xuejuan; Li, Cuihong; Wei, Hedi; Liu, Qian; Li, Weiwei; Bo, Zhishan

    2015-07-01

    Performance enhancement of polymer solar cells (PSCs) is achieved by expanding the absorption of the active layer of devices. To better match the spectrum of solar radiation, two polymers with different band gaps are used as the donor material to fabricate ternary polymer cells. Ternary blend PSCs exhibit an enhanced short-circuit current density and open-circuit voltage in comparison with the corresponding HD-PDFC-DTBT (HD)- and DT-PDPPTPT (DPP)-based binary polymer solar cells, respectively. Ternary PSCs show a power conversion efficiency (PCE) of 6.71%, surpassing the corresponding binary PSCs. This work demonstrates that the fabrication of ternary PSCs by using two polymers with complementary absorption is an effective way to improve the device performance.