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Sample records for absorption spectra fluorescence

  1. Simultaneous acquisition of absorption and fluorescence spectra of strong absorbers utilizing an evanescent supercontinuum.

    PubMed

    Kiefer, Johannes

    2016-12-15

    The determination of the absorption and emission spectra of strongly absorbing molecules is challenging, and the data can be biased by self-absorption of the fluorescence signal. To overcome this problem, a total internal reflection approach is proposed. The strongly absorbing sample is placed in an evanescent field of the radiation of a supercontinuum source. The collimated reflected light encodes the absorption spectrum, and the isotropic fluorescence emission is collected in a direction perpendicular to the surface at the same time. This ensures that the emitted light has a minimum possibility of self-absorption inside the sample.

  2. Absorption and fluorescence spectra of poly(p-phenylenevinylene) (PPV) oligomers: an ab initio simulation.

    PubMed

    Cardozo, Thiago M; Aquino, Adélia J A; Barbatti, Mario; Borges, Itamar; Lischka, Hans

    2015-03-05

    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.

  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 spectra and spectral-kinetic characteristics of the fluorescence of Sanguinarine in complexes with polyelectrolytes and DNA

    NASA Astrophysics Data System (ADS)

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

    2010-07-01

    The absorption spectra and stationary and time resolved fluorescence spectra of the isoquinoline alkaloid sanguinarine are studied in aqueous media and during interactions with synthetic polyelectrolytes (polystyrene sulfonate and polyallylamine) and a natural polyelectrolyte (DNA).

  5. In situ phytoplankton absorption, fluorescence emission, and particulate backscattering spectra determined from reflectance

    NASA Technical Reports Server (NTRS)

    Roesler, Collin S.; Pery, Mary Jane

    1995-01-01

    An inverse model was developed to extract the absortion and scattering (elastic and inelastic) properties of oceanic constituents from surface spectral reflectance measurements. In particular, phytoplankton spectral absorption coefficients, solar-stimulated chlorophyll a fluorescence spectra, and particle backscattering spectra were modeled. The model was tested on 35 reflectance spectra obtained from irradiance measurements in optically diverse ocean waters (0.07 to 25.35 mg/cu m range in surface chlorophyll a concentrations). The universality of the model was demonstrated by the accurate estimation of the spectral phytoplankton absorption coefficents over a range of 3 orders of magnitude (rho = 0.94 at 500 nm). Under most oceanic conditions (chlorophyll a less than 3 mg/cu m) the percent difference between measured and modeled phytoplankton absorption coefficents was less than 35%. Spectral variations in measured phytoplankton absorption spectra were well predicted by the inverse model. Modeled volume fluorescence was weakly correlated with measured chl a; fluorescence quantum yield varied from 0.008 to 0.09 as a function of environment and incident irradiance. Modeled particle backscattering coefficients were linearly related to total particle cross section over a twentyfold range in backscattering coefficents (rho = 0.996, n = 12).

  6. Solvent effects on the absorption and fluorescence spectra of rhaponticin: Experimental and theoretical studies

    NASA Astrophysics Data System (ADS)

    Sun, Yang; Liang, Xuhua; Zhao, Yingyong; Fan, Jun

    2013-02-01

    Rhaponticin (RH) possesses a variety of pharmacological activities including potent antitumor, antitumor-promoting, antithrombotic, antioxidant and vasorelaxant effects. The fundamental photophysics of RH is not well understood. In this work, solvent effect on the photoluminescence behavior of RH was studied by fluorescence and absorption spectra. The bathchromic shift was observed in absorption and fluorescence spectra with the increase of solvents polarity, which implied that transition involved was π → π*. A quantitative estimation of the contribution from different solvatochromic parameters, like normalized transition energy value (ETN), was made using the linear stokes shift (Δν) relationship based on the Lippert-Suppan equation. The ground state and excited state dipole moments were calculated by quantum-mechanical second-order perturbation method as a function of the dielectric constant (ɛ) and refractive index (n). The result was found to be 2.23 and 3.67 D in ground state and excited state respectively. The density functional theory (DFT) was used to obtain the most stable structure, electronic excitation energy, dipole moments and charge distribution. The analysis revealed that the RH exhibited strong photoinduced intramolecular charge transfer (ICT), and the intermolecular hydrogen bonding ability of the solvent was the most important parameter to characterize the photophysics behavior of RH. The hydrogen bonding effect occurred at the localized electron-acceptor oxygen at the glycoside bond. The experimental and theoretical results would help us better understand the photophysical properties of RH.

  7. Solvent effects on the steady-state absorption and fluorescence spectra of uracil, thymine and 5-fluorouracil.

    PubMed

    Gustavsson, Thomas; Sarkar, Nilmoni; Bányász, Akos; Markovitsi, Dimitra; Improta, Roberto

    2007-01-01

    We report a comparison of the steady-state absorption and fluorescence spectra of three representative uracil derivatives (uracil, thymine and 5-fluorouracil) in alcoholic solutions. The present results are compared with those from our previous experimental and computational studies of the same compounds in water and acetonitrile. The effects of solvent polarity and hydrogen bonding on the spectra are discussed in the light of theoretical predictions. This comparative analysis provides a more complete picture of the solvent effects on the absorption and fluorescence properties of pyrimidine nucleobases, with special emphasis on the mechanism of the excited state deactivation.

  8. Theoretical studies on the vibrationally-resolved absorption and fluorescence spectra of H-Pyrene+ and H-Coronene+

    NASA Astrophysics Data System (ADS)

    Li, JunFeng; Tian, GuanJun; Luo, Yi; Cao, ZeXing

    2015-11-01

    H-Pyrene+ and H-Coronene+ are important carrier candidates for the diffuse interstellar band. In order to understand the observed absorption and fluorescence emission spectra of H-Pyrene+ and H-Coronene+, time-dependent density functional theory (TD-DFT) method and Franck-Condon approximation have been employed to simulate the corresponding vibrationally-resolved optical spectra. For H-Pyrene+, the calculated absorption, emission and 0-0 band energies are in good agreement with the experimental values. The strong absorption and emission vibrational peaks near the 0-0 band match well with the experiment peaks. A noticeable deviation for several weak peaks far away from the origin band is observed, as a result of the vibronic coupling with other excited states. For H-Coronene+, the predicted vibrationally resolved electronic absorption and emission spectra resemble very well their experimental counterparts spectra, allowing to fully assign the observed vibronic peaks.

  9. Role of non-Condon vibronic coupling and conformation change on two-photon absorption spectra of green fluorescent protein

    NASA Astrophysics Data System (ADS)

    Ai, Yuejie; Tian, Guangjun; Luo, Yi

    2013-07-01

    Two-photon absorption spectra of green fluorescent proteins (GFPs) often show a blue-shift band compared to their conventional one-photon absorption spectra, which is an intriguing feature that has not been well understood. We present here a systematic study on one- and two-photon spectra of GFP chromophore by means of the density functional response theory and complete active space self-consistent field (CASSCF) methods. It shows that the popular density functional fails to provide correct vibrational progression for the spectra. The non-Condon vibronic coupling, through the localised intrinsic vibrational modes of the chromophore, is responsible for the blue-shift in the TPA spectra. The cis to trans isomerisation can be identified in high-resolution TPA spectra. Our calculations demonstrate that the high level ab initio multiconfigurational CASSCF method, rather than the conventional density functional theory is required for investigating the essential excited-state properties of the GFP chromophore.

  10. 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.

  11. 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.

  12. Multi-Photon Absorption Spectra: A Comparison Between Transmittance Change and Fluorescence Methods

    DTIC Science & Technology

    2015-05-21

    AFRL-OSR-VA-TR-2015-0134 multi-photon absorption spectra Cleber Mendonca INSTITUTO DE FISICA DE SAO CARLOS Final Report 05/21/2015 DISTRIBUTION A...5f. WORK UNIT NUMBER 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) Instituto de Fisica de Sao Carlos - Universidade de Sao Paulo Av...Trabalhador Saocarlense 400 Sao Carlos, SP, 13566-590 Brazil 8. PERFORMING ORGANIZATION REPORT NUMBER Report 3 - Final 9. SPONSORING/MONITORING AGENCY

  13. 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.

  14. [The absorption and fluorescence spectra of the cyanobacterial phycobilins of cryptoendolithic lichens in the high-polar region of Antarctica].

    PubMed

    Erokhina, L G; Shatilovich, A V; Kaminskaia, O P; Gilichinskiĭ, D A

    2002-01-01

    The algologically pure cultures of the green-brown cyanobacterium Chroococcidiopsis sp. and three cyanobacteria of the genus Gloeocapsa, the blue-green Gloeocapsa sp.1, the brown Gloeocapsa sp.2, and the red-orange Gloeocapsa sp.3, were isolated from sandstones and rock fissures in the high-polar regions of Antarctica. These cyanobacteria are the most widespread phycobionts of cryptoendolithic lichens in these regions. The comparative analysis of the absorption and the second-derivative absorption spectra of the cyanobacteria revealed considerable differences in the content of chlorophyll a and in the content and composition of carotenoids and phycobiliproteins. In addition to phycocyanin, allophycocyanin, and allophycocyanin B, which were present in all of the cyanobacteria studied, Gloeocapsa sp.2 also contained phycoerythrocyanin and Gloeocapsa sp.3 phycoerythrocyanin and C-phycoerythrin (the latter pigment is typical of nitrogen-fixing cyanobacteria). The fluorescence spectra of Gloeocapsa sp.2 and Gloeocapsa sp.3 considerably differed from the fluorescence spectra of the other cyanobacteria as well. The data obtained suggest that various zones of the lichens may be dominated either by photoheterotrophic or photoautotrophic cyanobacterial phycobionts, which differ in the content and composition of photosynthetic pigments.

  15. Excited state dipole moments of N, N-dimethylaniline from thermochromic effect on electronic absorption and fluorescence spectra

    NASA Astrophysics Data System (ADS)

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

    2006-01-01

    The effect of temperature on absorption and fluorescence spectra of N, N-dimethylaniline (DMA) in ethyl acetate has been studied for temperature ranging from 293 to 388 K. The permittivity ɛ and refractive index n of the solvent decrease with temperature increase and the absorption and fluorescence bands are blue shifted (so-called "thermochromic shift"). Based on this phenomenon, the dipole moment μe in the excited singlet state and the Onsager interaction radius a for DMA were determined using the Bilot and Kawski theory [L. Bilot, A. Kawski, Z. Naturforsch. 17a (1962) 621; 18a (1963) 10, 256]. For the known dipole moment in the ground state μg = 1.61 D and for α/ a3 = 0.54 ( α is the polarizability of the solute) the average value of μe = 3.55 D and a = 3.1 Å were determined. The obtained values for DMA are compared with the experimental values determined by other authors.

  16. 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.

  17. Anharmonic Franck-Condon simulation of the absorption and fluorescence spectra for the low-lying S1 and S2 excited states of pyridine.

    PubMed

    Wang, Huan; Zhu, Chaoyuan; Yu, Jian-Guo; Lin, Sheng Hsien

    2009-12-31

    Anharmonic effects of the absorption and fluorescence spectra of pyridine molecule are studied and analyzed for the two-low lying singlet excited states S(1)((1)B(1)) and S(2)((1)B(2)). The complete active space self-consistent field (CASSCF) method is utilized to compute equilibrium geometries and all 27 vibrational normal-mode frequencies for the ground state and the two excited states. The present calculations show that the frequency differences between the ground and two excited states are small for the ten totally symmetric vibrational modes so that the displaced oscillator approximation can be used for spectrum simulations. The Franck-Condon factors within harmonic approximation basically grasp the main features of molecular spectra, but simulated 0-0 transition energy position and spectrum band shapes are not satisfactorily good for S(1)((1)B(1)) absorption and fluorescence spectra in comparison with experiment observation. As the first-order anharmonic correction added to Franck-Condon factors, both spectrum positions and band shapes can be simultaneously improved for both absorption and fluorescence spectra. It is concluded that the present anharmonic correction produces a significant dynamic shifts for spectrum positions and improves spectrum band shapes as well. The detailed structures of absorption spectrum of S(2)((1)B(2)) state observed from experiment can be also reproduced with anharmonic Franck-Condon simulation, and these were not shown in the harmonic Franck-Condon simulation with either distorted or Duschinsky effects in the literature.

  18. Franck-Condon factors perturbed by damped harmonic oscillators: Solvent enhanced X 1Ag ↔ A1B1u absorption and fluorescence spectra of perylene

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

    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 1Ag ↔ A1B1u absorption and fluorescence spectra of perylene (medium-sized polycyclic aromatic hydrocarbon) in benzene solution. It is found that one of six active normal modes v10 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.

  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

    2016-09-08

    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. 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.

  1. Estimation of ground- and excited-state dipole moments of Nile Red dye from solvatochromic effect on absorption and fluorescence spectra

    NASA Astrophysics Data System (ADS)

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

    2008-10-01

    The effect of various nonpolar and polar solvents on the location of absorption and fluorescence of Nile Red at room temperature was investigated. Based on the batochromic shift of electronic spectra of Nile Red and Bilot-Kawski theory the following values of ground- and excited-state dipole moments μg = 8.2 ± 1.0 D and μe = 10.0 ± 1.0 D were found. The reasons of high discrepancy between the literature results were discussed.

  2. Absorption, Fluorescence and Emission Anisotropy Spectra of 4-Cyano-N,N-dimethylaniline in Different Media and at Different Temperatures

    NASA Astrophysics Data System (ADS)

    Kawski, A.; Piszczek, G.

    1997-05-01

    The effect of temperature on fluorescence and emission anisotropy spectra of 4-cyano-N,N-dimethylaniline (CDMA) was investigated in viscous (glycerol and paraffin oil) and rigid (polyvinyl alcohol) PVA and polyvinyl chloride) PVC) media. A strong effect of temperature on the intensity of a and b emission bands was observed. It was also found that the emission anisotropy, r, does not vary in the longwave emission band a at a fixed temperature but decreases in the emission band b together with the decreasing wavelength. The latter effect is due to the fact that the transition moment in this band is perpendicular to the long axis of the CDMA molecule. For CDMA in paraffin oil, a normal b band with negative emission anisotropy only occurs. In all other media used, the emission anisotropy has lower values, approaching zero, which results from the considerable covering of band b with a broad emission band a.

  3. Effects of solvent polarity on the absorption and fluorescence spectra of chlorogenic acid and caffeic acid compounds: determination of the dipole moments.

    PubMed

    Belay, Abebe; Libnedengel, Ermias; Kim, Hyung Kook; Hwang, Yoon-Hwae

    2016-02-01

    The effects of solvent polarity on absorption and fluorescence spectra of biologically active compounds (chlorogenic acid (CGA) and caffeic acids (CA)) have been investigated. In both spectra pronounced solvatochromic effects were observed with shift of emission peaks larger than the corresponding UV-vis electronic absorption spectra. From solvatochromic theory the ground and excited-state dipole moments were determined experimentally and theoretically. The differences between the excited and ground state dipole moment determined by Bakhshiev, Kawski-Chamma-Viallet and Reichardt equations are quite similar. The ground and excited-state dipole moments were determined by theoretical quantum chemical calculation using density function theory (DFT) method (Gaussian 09) and were also similar to the experimental results. The HOMO-LUMO energy band gaps for CGA and CFA were calculated and found to be 4.1119 and 1.8732 eV respectively. The results also indicated the CGA molecule is more stable than that of CFA. It was also observed that in both compounds the excited state possesses a higher dipole moment than that of the ground state. This confirms that the excited state of the hydroxycinnamic compounds is more polarized than that of the ground state and therefore is more sensitive to the solvent.

  4. Discrimination of petroleum fluorescence spectra.

    PubMed

    Stelmaszewski, Adam

    2007-01-01

    This paper presents studies of the total spectra (fluorescence-excitation matrix) of petroleum with regard to the utilization of fluorescence for determining petroleum pollutants. Thorough testing of one group, comprising almost forty lubricating oils in the form of their hexane solutions, points out their discrimination.

  5. The action of oxygen on chlorophyll fluorescence quenching and absorption spectra in pea thylakoid membranes under the steady-state conditions.

    PubMed

    Garstka, Maciej; Nejman, Patrycja; Rosiak, Małgorzata

    2004-12-02

    The effect of oxygen concentration on both absorption and chlorophyll fluorescence spectra was investigated in isolated pea thylakoids at weak actinic light under the steady-state conditions. Upon the rise of oxygen concentration from anaerobiosis up to 412 microM a gradual absorbance increase around both 437 and 670 nm was observed, suggesting the disaggregation of LHCII and destacking of thylakoids. Simultaneously, an increase in oxygen concentration resulted in a decline in the Chl fluorescence at 680 nm to about 60% of the initial value. The plot of normalized Chl fluorescence quenching, F(-O(2))/F(+O(2)), showed discontinuity above 275 microM O(2), revealing two phases of quenching, at both lower and higher oxygen concentrations. The inhibition of photosystem II by DCMU or atrazine as well as that of cyt b(6)f by myxothiazol attenuated the oxygen-induced quenching events observed above 275 microM O(2), but did not modify the first phase of oxygen action. These data imply that the oxygen mediated Chl fluorescence quenching is partially independent on non-cyclic electron flow. The second phase of oxygen-induced decline in Chl fluorescence is diminished in thylakoids with poisoned PSII and cyt b(6)f activities and treated with rotenone or N-ethylmaleimide to inhibit NAD(P)H-plastoquinone dehydrogenase. The data suggest that under weak light and high oxygen concentration the Chl fluorescence quenching results from interactions between oxygen and PSI, cyt b(6)f and Ndh. On the contrary, inhibition of non-cyclic electron flow by antimycin A or uncoupling of thylakoids by carbonyl cyanide m-chlorophenyl hydrazone did not modify the steady-state oxygen effect on Chl fluorescence quenching. The addition of NADH protected thylakoids against oxygen-induced Chl fluorescence quenching, whereas in the presence of exogenic duroquinone the decrease in Chl fluorescence to one half of the initial level did not result from the oxygen effect, probably due to oxygen action as a

  6. [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.

  7. 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.

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

    PubMed

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

    2016-02-05

    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 (μ(e)). It is observed that dipole moment value of excited state (μ(e)) 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.

  9. Quantitative treatment of the solvent effects on the electronic absorption and fluorescence spectra of acridines and phenazines. The ground and first excited singlet-state dipole moments

    NASA Astrophysics Data System (ADS)

    Aaron, Jean Jacques; Maafi, Mounir; Párkányi, Cyril; Boniface, Christian

    1995-04-01

    Electronic absorption and fluorescence excitation and emission spectra of four acridines (acridine, Acridine Yellow, 9-aminoacridine and proflavine) and three phenazines (phenazine, neutral Red and safranine) are determined at room temperature (298 K) in several solvents of various polarities (dioxane, chloroform, ethyl ether, ethyl acetate, 1-butanol, 2-propanol, ethanol, methanol, dimethylformamide, acetonitrile and dimethyl sulfoxide). The effect of the solvent upon the spectral characteristics of the above compounds, is studied. In combination with the ground-state dipole moments of these compounds, the spectral data are used to evaluate their first excited singlet-state dipole moments by means of the solvatochromic shift method (Bakhshiev's and Kawski-Chamma-Viallet's correlations). The theoretical ground and excited singlet-state dipole moments for acridines and phenazines are also calculated as a vector sum of the π-component (obtained by the PPP method) and the σ-component (obtained from σ-bond moments). For most acridines and phenazines under study, the experimental excited singlet-state dipole moments are found to be higher than their ground state counterpart. The application of the Kamlet-Abboud-Taft solvatochromic parameters to the solvent effect on spectral properties of acridine and phenazine derivatives is discussed.

  10. Solvent effect on the absorption and fluorescence spectra of 7-acetoxy-6-(2,3-dibromopropyl)-4,8-dimethylcoumarin: determination of ground and excited state dipole moments.

    PubMed

    Gülseven Sıdır, Yadigar; Sıdır, Isa

    2013-02-01

    The ground state (μ(g)) and excited state (μ(e)) dipole moments of 7-acetoxy-6-(2,3-dibromopropyl)-4,8-dimethylcoumarin (abbreviated as 7ADDC) are estimated from solvatochromic shifts of absorption and fluorescence spectra as a function of the dielectric constant (ε) and refractive index (n). While the ground state dipole moment is determined by using Bilot-Kawski method, the excited state dipole moment is calculated by using Bilot-Kawski, Lippert-Mataga, Bakhshiev, Kawski-Chamma-Viallet and Reichardt correlation methods. Excited state dipole moment is observed as larger than the ground state dipole moment due to substantial π-electron density redistribution. The ground state and excited state dipole moments are observed as parallel to each other with angle of 0°. Solute-solvent interactions are analyzed by means of linear solvation free energy relationships (LSER) using dielectric constant function (f(ε)), refractive index function (f(n)) and Kamlet-Taft parameters (α and β). Atomic charges, electron densities and molecular orbitals are calculated in vacuum and with solvent effect by using both DFT and TDDFT methods. Solvent accessible surface, molecular electrostatic potential (MEP) and electrostatic potential (ESP) are visualized as a result of DFT calculations.

  11. Quantitative treatment of the effect of solvent on the electronic absorption and fluorescence spectra of substituted coumarins: Evaluation of the first excited singlet-state dipole moments.

    PubMed

    Aaron, J J; Buna, M; Parkanyi, C; Antonious, M S; Tine, A; Cisse, L

    1995-12-01

    The electronic absorption and fluorescence spectra of coumarin and 11 substituted coumarins were measured in several solvents (dioxane, ethyl ether, ethyl acetate, ethanol, dimethylformamide, acetonitrile, and dimethyl sulfoxide). Ground-state dipole moments were determined in dioxane at 298 K. The results were used to obtain the first excited singlet-state dipole moments of the coumarins under study by the solvatochromic shift method (Bakhshiev, Kawski-Chamma-Viallet, McRae, and Suppan correlations). Also, the ground- and the first excited singlet-state dipole moments were calculated using a combination of the PPP method (π-contribution) and the vector sum of the σ-bond and group moments (σ-contribution). In general, the first excited singlet-state dipole moments of the coumarins are noticeably higher than the corresponding ground-state values, indicating a substantial redistribution of theπ-electron densities resulting in a more polar excited state. There is a reasonably good agreement between the calculated and the experimental dipole moments.

  12. Solvent effects on the absorption and fluorescence spectra of some laser dyes: estimation of ground and excited-state dipole moments.

    PubMed

    Thipperudrappa, J; Biradar, D S; Manohara, S R; Hanagodimath, S M; Inamadar, S R; Manekutla, R J

    2008-03-01

    The absorption and fluorescence spectra of three extensively used laser dyes namely 1,1,4,4-tetraphenyl-1,3-butadiene (TPB), 2-(4'-t-butylphenyl)-5-(4''-biphenylyl)-1-oxa-3,4-diazole (BPBD), 1,4-bis[2-(2-methylphenyl)ethenyl]-benzene (Bis-MSB) have been recorded at room temperature (300K) in solvents of different polarities. The effects of the solvents upon the spectral properties are discussed. The ground-state dipole moments (mu(g)) were determined experimentally by Guggenheim and Higasi method separately and were compared with theoretical values obtained using quantum chemical method. The ground-state dipole moments obtained by using Guggenheim method were then used in the estimation of excited-state dipole moments (mu(e)) by using Lippert's, Bakhshiev's and Kawski-Chamma-Viallet's equations. In all the above three equations the variation of the Stokes shift with the solvent dielectric constant and refractive index was made use of. It was observed that dipole moments of excited state were higher than those of the ground state for all the dyes.

  13. Solvent effect on the absorption and fluorescence spectra of 7-acetoxy-6-(2,3-dibromopropyl)-4,8-dimethylcoumarin: Determination of ground and excited state dipole moments

    NASA Astrophysics Data System (ADS)

    Gülseven Sıdır, Yadigar; Sıdır, İsa

    2013-02-01

    The ground state (μg) and excited state (μe) dipole moments of 7-acetoxy-6-(2,3-dibromopropyl)-4,8-dimethylcoumarin (abbreviated as 7ADDC) are estimated from solvatochromic shifts of absorption and fluorescence spectra as a function of the dielectric constant (ɛ) and refractive index (n). While the ground state dipole moment is determined by using Bilot-Kawski method, the excited state dipole moment is calculated by using Bilot-Kawski, Lippert-Mataga, Bakhshiev, Kawski-Chamma-Viallet and Reichardt correlation methods. Excited state dipole moment is observed as larger than the ground state dipole moment due to substantial π-electron density redistribution. The ground state and excited state dipole moments are observed as parallel to each other with angle of 0°. Solute-solvent interactions are analyzed by means of linear solvation free energy relationships (LSER) using dielectric constant function (f(ɛ)), refractive index function (f(n)) and Kamlet-Taft parameters (α and β). Atomic charges, electron densities and molecular orbitals are calculated in vacuum and with solvent effect by using both DFT and TDDFT methods. Solvent accessible surface, molecular electrostatic potential (MEP) and electrostatic potential (ESP) are visualized as a result of DFT calculations.

  14. Solvent effects on the absorption and fluorescence spectra of some laser dyes: Estimation of ground and excited-state dipole moments

    NASA Astrophysics Data System (ADS)

    Thipperudrappa, J.; Biradar, D. S.; Manohara, S. R.; Hanagodimath, S. M.; Inamadar, S. R.; Manekutla, R. J.

    2008-03-01

    The absorption and fluorescence spectra of three extensively used laser dyes namely 1,1,4,4-tetraphenyl-1,3-butadiene (TPB), 2-(4'- t-butylphenyl)-5-(4″-biphenylyl)-1-oxa-3,4-diazole (BPBD), 1,4-bis[2-(2-methylphenyl)ethenyl]-benzene (Bis-MSB) have been recorded at room temperature (300 K) in solvents of different polarities. The effects of the solvents upon the spectral properties are discussed. The ground-state dipole moments ( μg) were determined experimentally by Guggenheim and Higasi method separately and were compared with theoretical values obtained using quantum chemical method. The ground-state dipole moments obtained by using Guggenheim method were then used in the estimation of excited-state dipole moments ( μe) by using Lippert's, Bakhshiev's and Kawski-Chamma-Viallet's equations. In all the above three equations the variation of the Stokes shift with the solvent dielectric constant and refractive index was made use of. It was observed that dipole moments of excited state were higher than those of the ground state for all the dyes.

  15. 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.

  16. 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.

  17. 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

  18. On optimization of absorption-dispersion spectra

    NASA Astrophysics Data System (ADS)

    Hawranek, J. P.; Grabska, J.; Beć, K. B.

    2016-12-01

    A modified approach to the analysis of spectra of the complex electric permittivity of liquids in the Infrared region is presented. These spectra are derived from experimental spectra of the complex refractive index. Subsequently they are used to determine important secondary quantities, e.g. spectra of complex molecular polarizabilities and an integral property - the molar vibrational polarization. The accuracy of these quantities depends essentially on the accuracy of both components of the complex electric permittivity spectrum. In the proposed procedure, the spectra of the complex electric permittivity are approximated using the Classical Damped Harmonic Oscillator (CDHO) model for the description of individual bandshapes. The CDHO model defines both the real and imaginary part of the complex permittivity. The fitting procedure includes a simultaneous optimization of both the real and imaginary parts of the complex permittivity spectrum. A comparison of absorption-only curve fitting and the novel absorption-dispersion double curve fitting is presented; advantages of the new approach in accuracy, reliability and convergence time are pointed out. Due to the complexity of the problem, the choice was restricted to non-gradient methods of optimization. The performance of several gradientless algorithms was tested. Among numerous procedures the Powell General Least Squares Method Without Derivatives was found to be the most efficient. The reliability of obtained results of the band separatiovn process was tested on several simulated spectra of increasing complexity. The applicability of the developed approach to the analysis of exemplary experimental data was evaluated and discussed.

  19. Terahertz absorption spectra of highly energetic chemicals

    NASA Astrophysics Data System (ADS)

    Slingerland, E. J.; Vallon, M. K.; Jahngen, E. G. E.; Giles, R. H.; Goyette, T. M.

    2010-04-01

    Research into absorption spectra is useful for detecting chemicals in the field. Each molecule absorbs a set of specific frequencies, which are dependent on the molecule's structure. While theoretical models are available for predicting the absorption frequencies of a particular molecule, experimental measurements are a more reliable method of determining a molecule's actual absorption behavior. The goal of this research is to explore chemical markers (absorption frequencies) that can be used to identify highly energetic molecules of interest to the remote sensing community. Particular attention was paid to the frequency ranges located within the terahertz transmission windows of the atmosphere. In addition, theoretical derivations, with the purpose of calculating the detection limits of such chemicals, will also be presented.

  20. Fluorescence polarization and dichroic spectra of stilbene derivatives

    SciTech Connect

    Nekadamov, S.; Senyuk, M.A.; Bobrovich, V.P.

    1987-09-01

    Fluorescence polarization spectra were measured by means of the single photon counting technique with the use of a setup comprising two quartz monochromators. The relative experiment error did not exceed 3% for polarizations close to the limiting value of 6% for p approx. 0.1. Dichroic spectra of stilbene derivatives were measured with a Specord UV-VIS spectrophotometer. The polarization of the fluorescence emission band for the oxazole derivatives of stilbene is practically constant exhibiting slight increases in the vibration maxima. This polarization behavior indicates that the emission is due to a single electronic transition. The absorption spectra of the oxazole derivatives of stilbene contain three broad bands in the near-UV region. The long-wavelength absorption band (A band) is due to the excitation of the entire ..pi..-electron system of the molecule. Phenyl and oxazole rings lead to the appearance of a new absorption band (R band) with the maximum near 290 nm. The short-wavelength B band is due to the ..pi..-excitation of the benzene rings.

  1. 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.

  2. Equilibria and absorption spectra of tryptophanase.

    PubMed

    Metzler, C M; Viswanath, R; Metzler, D E

    1991-05-25

    Tryptophanase (tryptophan: indole-lyase) from Escherichia coli has been isolated in the holoenzyme form and its absorption spectra and acid-base chemistry have been reevaluated. Apoenzyme has been prepared by dialysis against sodium phosphate and L-alanine and molar absorptivities of the coenzyme bands have been estimated by readdition of pyridoxal 5'-phosphate. The spectrophotometric titration curve, whose midpoint is at pH 7.6 in 0.1 M potassium phosphate buffers, indicates some degree of cooperativity in dissociation of a pair of protons. Resolution of the computed spectra of individual ionic forms of the enzyme with lognormal distribution curves shows that band shapes are similar to those of model Schiff bases and of aspartate aminotransferase. Using molar areas from the latter we estimated amounts of individual tautomeric species. In addition to ketoenamine and enolimine or covalent adduct the high pH form also appears to contain approximately 18% of a species with a dipolar ionic ring (protonated on the ring nitrogen and with phenolate -O-). We suggest that this may be the catalytically active form of the coenzyme in tryptophanase. The equilibrium between tryptophanase and L-alanine has also been reevaluated.

  3. Millimeter wave absorption spectra of biological samples

    SciTech Connect

    Gandhi, O.P.; Hagmann, M.J.; Hill, D.W.; Partlow, L.M.; Bush, L.

    1980-01-01

    A solid-state computer-controlled system has been used to make swept-frequency measurements of absorption of biological specimens from 26.5 to 90.0 GHz. A wide range of samples was used, including solutions of DNA and RNA, and suspensions of BHK-21/C13 cells, Candida albicans, C krusei, and Escherichia coli. Sharp spectra reported by other workers were not observed. The strong absorbance of water (10--30 dB/mm) caused the absorbance of all aqueous preparations that we examined to have a water-like dependence on frequency. Reduction of incident power (to below 1.0 microW), elimination of modulation, and control of temperature to assure cell viability were not found to significantly alter the water-dominated absorbance. Frozen samples of BHK-21/C13 cells tested at dry ice and liquid nitrogen temperatures were found to have average insertion loss reduced to 0.2 dB/cm but still showed no reproducible peaks that could be attributed to absorption spectra. It is concluded that the special resonances reported by others are likely to be in error.

  4. Computer Modeling of the Structure and Spectra of Fluorescent Proteins

    PubMed Central

    Grigorenko, B.L.; Savitsky, A.P.

    2009-01-01

    Fluorescent proteins from the family of green fluorescent proteins are intensively used as biomarkers in living systems. The chromophore group based on the hydroxybenzylidene-imidazoline molecule, which is formed in nature from three amino-acid residues inside the protein globule and well shielded from external media, is responsible for light absorption and fluorescence. Along with the intense experimental studies of the properties of fluorescent proteins and their chromophores by biochemical, X-ray, and spectroscopic tools, in recent years, computer modeling has been used to characterize their properties and spectra. We present in this review the most interesting results of the molecular modeling of the structural parameters and optical and vibrational spectra of the chromophorecontaining domains of fluorescent proteins by methods of quantum chemistry, molecular dynamics, and combined quantum-mechanical-molecular-mechanical approaches. The main emphasis is on the correlation of theoretical and experimental data and on the predictive power of modeling, which may be useful for creating new, efficient biomarkers. PMID:22649601

  5. Neural Network Solutions to Optical Absorption Spectra

    NASA Astrophysics Data System (ADS)

    Rosenbrock, Conrad

    2012-10-01

    Artificial neural networks have been effective in reducing computation time while achieving remarkable accuracy for a variety of difficult physics problems. Neural networks are trained iteratively by adjusting the size and shape of sums of non-linear functions by varying the function parameters to fit results for complex non-linear systems. For smaller structures, ab initio simulation methods can be used to determine absorption spectra under field perturbations. However, these methods are impractical for larger structures. Designing and training an artificial neural network with simulated data from time-dependent density functional theory may allow time-dependent perturbation effects to be calculated more efficiently. I investigate the design considerations and results of neural network implementations for calculating perturbation-coupled electron oscillations in small molecules.

  6. 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.

  7. A quantitative study of the effect of solvent on the electronic absorption and fluorescence spectra of substituted phenothiazines: evaluation of their ground and excited singlet-state dipole moments

    NASA Astrophysics Data System (ADS)

    Párkányi, C.; Boniface, C.; Aaron, J. J.; Maafi, M.

    1993-11-01

    Electronic absorption and fluorescence excitation and emission spectra of five phenothiazines (phenothiazine, promethazine, thionine, methylene blue and Azure A) were determined at room temperature (293 K) in several solvents of various polarities (cyclohexane, dioxane, ethyl ether, chloroform, ethyl acetate, 1-butanol, 2-propanol, ethanol, methanol, acetonitrile, dimethylformamide and dimethyl sulfoxide). The effect of the solvents upon the spectral characteristics was studied. In combination with the ground state dipole moments of these phenothiazines, the spectral data were used to evaluate their first excited singlet-state dipole moments by means of the solvatochromic shift method (Bakhshiev's and Kawski—Chamma—Viallet correlations). The theoretical ground and excited singlet-state dipole moments for phenothiazines were calculated as a vector sum of the π component (obtained by the Pariser—Parr—Pople method) and the σ component (obtained from σ-bond moments). A reasonable agreement was found with the experimental values. For most phenothiazines under study, excited singlet-state dipole moments were found to be significantly higher than their ground-state counterparts. The application of the Kamlet—Abboud—Taft solvatochromic parameters to the solvent effect on spectral properties of phenothiazines is discussed.

  8. Solvent effect on absorption and fluorescence spectra of three biologically active carboxamides (C1, C2 and C3). Estimation of ground and excited state dipole moment from solvatochromic method using solvent polarity parameters.

    PubMed

    Patil, N R; Melavanki, R M; Kapatkar, S B; Ayachit, N H; Saravanan, J

    2011-05-01

    The absorption and fluorescence spectra of three Carboxamides namely (E)-2-(4-Chlorobenzylideneamino)-N-(2-chlorophenyl)-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carboxamide (C(1)), (E)-N-(3-Chlorophenyl)-2-(3, 4-dimethoxybenzylideneamino)-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carboxamide (C(2)) and (E)-N-(3-Chlorophenyl)-2-(3,4,5-trimethoxybenzylideneamino)-4,5,6,7-tetrahydrobenzo[b]thiophene-3-carboxamide (C(3)) have been recorded at room temperature in solvents of different polarities using dielectric constant (ε) and refractive index (n). Experimental ground (μ(g)) and excited (μ(e)) state dipole moments are estimated by means of solvatochromic shift method and also the excited dipole moments are estimated in combination with ground state dipole moments. It was estimated that dipole moments of the excited state were higher than those of the ground state of all three molecules. Further, the changes in dipole moment (Δμ) were calculated both from solvatochromic shift method and on the basis of microscopic empirical solvent polarity parameter (E(N)(T)) and the values are compared.

  9. Electronic absorption spectra from first principles

    NASA Astrophysics Data System (ADS)

    Hazra, Anirban

    Methods for simulating electronic absorption spectra of molecules from first principles (i.e., without any experimental input, using quantum mechanics) are developed and compared. The electronic excitation and photoelectron spectra of ethylene are simulated, using the EOM-CCSD method for the electronic structure calculations. The different approaches for simulating spectra are broadly of two types---Frank-Condon (FC) approaches and vibronic coupling approaches. For treating the vibrational motion, the former use the Born-Oppenheimer or single surface approximation while the latter do not. Moreover, in our FC approaches the vibrational Hamiltonian is additively separable along normal mode coordinates, while in vibronic approaches a model Hamiltonian (obtained from ab initio electronic structure theory) provides an intricate coupling between both normal modes and electronic states. A method called vertical FC is proposed, where in accord with the short-time picture of molecular spectroscopy, the approximate excited-state potential energy surface that is used to calculate the electronic spectrum is taken to reproduce the ab initio potential at the ground-state equilibrium geometry. The potential energy surface along normal modes may be treated either in the harmonic approximation or using the full one-dimensional potential. Systems with highly anharmonic potential surfaces can be treated and expensive geometry optimizations are not required, unlike the traditional FC approach. The ultraviolet spectrum of ethylene between 6.2 and 8.7 eV is simulated using vertical FC. While FC approaches for simulation are computationally very efficient, they are not accurate when the underlying approximations are unreasonable. Then, vibronic coupling model Hamiltonians are necessary. Since these Hamiltonians have an analytic form, they are used to map the potential energy surfaces and understand their topology. Spectra are obtained by numerical diagonalization of the Hamiltonians. The

  10. Computed survey spectra of 2-5 micron atmospheric absorption

    NASA Astrophysics Data System (ADS)

    Leslie, D. H.; Lebow, P. S.

    1983-08-01

    Computed high resolution survey spectra of atmospheric absorption coefficient vs wavenumber are presented covering the wavelength region 2-5 micrometers. The 1980 AFGL atmospheric absorption parameter compilation was employed with a mid-latitude, sea-level atmospheric model.

  11. Anomalous atmospheric absorption spectra due to water dimer

    NASA Astrophysics Data System (ADS)

    Cai, Peipei; Zhang, Hansheng; Shen, Shanxiong; Cheng, I.-Shan

    1986-11-01

    The anomalous atmospheric absorption spectra in the window wavelength region of 8-14 microns have been suggested due to the water dimer. Based on laboratory measurements, water continuum CO2 laser absorption spectra and a resonance absorption line due to the weak local wave vapor pure rotational transition have been reported. The equilibrium concentration of water dimers in the atmosphere, the electronic binding energy and the theoretical calculations for absorption attenuation have been obtained in agreement with published data.

  12. 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

  13. A catalogue of absorption-line systems in QSO spectra

    NASA Astrophysics Data System (ADS)

    Ryabinkov, A. I.; Kaminker, A. D.; Varshalovich, D. A.

    2003-12-01

    We present a new catalog of absorption-line systems identified in the quasar spectra. It contains data on 821 QSOs and 8558 absorption systems comprising 16 139 absorption lines with measured redshifts in the QSO spectra. The catalog includes absorption-line systems consisting of lines of heavy elements, lines of neutral hydrogen, Lyman limit systems, damped Lyα absorption systems, and broad absorption-line systems. Using the data of the present catalog we also discuss redshift distributions of absorption-line systems. Tables 1 and 2 are only available in electronic form at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsweb.u-strasbg.fr/cgi-bin/qcat?J/A+A/412/707

  14. Absorption and fluorescent spectral studies of imidazophenazine derivatives

    NASA Astrophysics Data System (ADS)

    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 3.7 D, respectively. The changes in dipole moments upon the optical excitation for all derivatives estimated using Lippert equation were found to be Δ μ=9 D. The energies of the electronic S 1←S 0 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.

  15. Absorption and Fluorescence Lineshape Theory for Polynomial Potentials.

    PubMed

    Anda, André; De Vico, Luca; Hansen, Thorsten; Abramavičius, Darius

    2016-12-13

    The modeling of vibrations in optical spectra relies heavily on the simplifications brought about by using harmonic oscillators. However, realistic molecular systems can deviate substantially from this description. We develop two methods which show that the extension to arbitrarily shaped potential energy surfaces is not only straightforward, but also efficient. These methods are applied to an electronic two-level system with potential energy surfaces of polynomial form and used to study anharmonic features such as the zero-phonon line shape and mirror-symmetry breaking between absorption and fluorescence spectra. The first method, which constructs vibrational wave functions as linear combinations of the harmonic oscillator wave functions, is shown to be extremely robust and can handle large anharmonicities. The second method uses the cumulant expansion, which is readily solved, even at high orders, thanks to an ideally suited matrix theorem.

  16. Absorption-Edge-Modulated Transmission Spectra for Water Contaminant Monitoring

    DTIC Science & Technology

    2016-03-31

    Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/6390--16-9675 Absorption-Edge-Modulated Transmission Spectra for Water Contaminant...ABSTRACT c. THIS PAGE 18. NUMBER OF PAGES 17. LIMITATION OF ABSTRACT Absorption-Edge-Modulated Transmission Spectra for Water Contaminant Monitoring...Unlimited Unclassified Unlimited 35 Samuel G. Lambrakos (202) 767-2601 Monitoring of contaminants associated with specific water resources using

  17. 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.

  18. Deconvolution of CPM absorption spectra: A new technique

    NASA Astrophysics Data System (ADS)

    Jensen, Pablo

    1990-12-01

    We have found a new technique for deconvoluting absorption spectra obtained with the constant photocurrent method on hydrogenated amorphous silicon samples. We have shown that our method is simpler and more accurate than those used until now. Finally, examples of spectra deconvolution for one sample after various thermal treatments are provided.

  19. Mid-infrared FEL absorption spectra

    NASA Astrophysics Data System (ADS)

    Kozub, John A.; Feng, Bibo; Gabella, William E.

    2002-04-01

    The Vanderbilt Mark III FEL is a tunable source of high- intensity coherent mid-infrared radiation occurring as a train of picosecond pulses spaced 350ps apart. The laser beam is transported to each laboratory under vacuum, but is typically transmitted through some distance of atmosphere before reaching the target. Losses due to absorption by water vapor and CO2 can be large, and since the bandwidth of the FEL is several percent of the wavelength, the spectrum can be altered by atmospheric absorptions. In order to provide an accurate representation of the laser spectrum delivered to the target, and to investigate any non-linear effects associated with transport of the FEL beam, we have recorded the spectrum of the FEL output using a vacuum spectrometer positioned after measured lengths of atmosphere. The spectrometer is equipped with a linear pyroelectric array which provides the laser spectrum for each pulse. Absorption coefficients are being measured for laboratory air, averaged over the bandwidth of the FEL. The high peak powers of this Fel have induced damage in common infrared-transparent materials; we are also measuring damage thresholds for several materials at various wavelengths.

  20. 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

    2013-06-04

    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.

  1. 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.

  2. 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.

  3. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

    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.

  5. Absorption and fluorescence properties of aryl substituted porphyrins in different media

    NASA Astrophysics Data System (ADS)

    Bozkurt, Serap Seyhan; Merdivan, Melek; Ayata, Sevda

    2010-02-01

    Absorption and fluorescence properties of aryl substituted porphyrins, 5,10,15,20-tetra-4-oxy(aceticacid)phenylporphyrin (TAPP), 5,10,15,20-tetra-(4-phenoxyphenyl) porphyrin (TPPP), 5,10,15,20-tetra-(3-bromo-4-hydroxyphenyl) porphyrin (TBHPP), and 5,10,15,20-tetra-p-chloromethylphenyl porphyrin (CMPP) were investigated. The UV/vis absorption, fluorescence and excited spectra as the fluorescence quantum yields and fluorescence lifetimes for the compounds were measured in organic solvents (chloroform (CHCl 3), tetrahydrofuran (THF)) and immobilized media (PVC film, sol-gel matrix). The fluorescence quantum yields of TAPP and TPPP were higher than the others. The fluorescence lifetimes of all studied porphyrin derivates were found to be fifty percent lower and their fluorescence intensities were increased fifty percent more in both of immobilized mediums, as compared to organic solvents.

  6. 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.

  7. 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.

  8. Ultraviolet absorption spectra of metalorganic molecules diluted in hydrogen gas

    NASA Astrophysics Data System (ADS)

    Itoh, Hideo; Watanabe, Masanobu; Mukai, Seiji; Yajima, Hiroyoshi

    1988-12-01

    Ultraviolet absorption spectra of trimethyl gallium, triethyl gallium, and trimethyl aluminum diluted in hydrogen gas were measured as a function of the wavelength (185-350 nm) and the concentration of the molecules (4.8×10 -6 -1.6×10 -4 mol/liter). Their absorbances changed linearly with the concentration of the molecules, which allowed us to calculate the molar absorption coefficients of the molecules on the basis of the Beer-Lambert law.

  9. 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.

  10. 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).

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

    PubMed

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

    2015-01-01

    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).

  12. [Ultraviolet absorption spectra of iodine, iodide ion and triiodide ion].

    PubMed

    Wei, Yong-Ju; Liu, Cui-Ge; Mo, Li-Ping

    2005-01-01

    Ultraviolet absorption spectra of iodine I2, iodide ion I(-) and triiodide ion I3(-) were studied, and molar absorptivities of these species were determined. Absorption spectrum of I2 aqueous solution appears as an absorption peak at 203 nm with a molar absorptivity of 1.96 x 10(4) L x mol(-1) x cm(-1). Absorption spectrum of I(-) appears as two absorption peaks at 193 and 226 nm with molar absorptivities of 1.42 x 10(4) and 1.34 x 10(4) L x mol(-1) x cm(-1), respectively. When I2 aqueous solution is mixed with KI solution, two absorption peaks appear at 288 and 350 nm, respectively, indicating the formation of I3(-). Using saturation method, molar absorptivities of I3(-) at 288 and 350 nm were determined to be 3.52 x 10(4) and 2.32 x 10(4) L x mol(-1) x cm(-1), respectively.

  13. 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.

  14. 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.

  15. 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…

  16. Accurate modeling of fluorescence line narrowing difference spectra: Direct measurement of the single-site fluorescence spectrum

    NASA Astrophysics Data System (ADS)

    Reppert, Mike; Naibo, Virginia; Jankowiak, Ryszard

    2010-07-01

    Accurate lineshape functions for modeling fluorescence line narrowing (FLN) difference spectra (ΔFLN spectra) in the low-fluence limit are derived and examined in terms of the physical interpretation of various contributions, including photoproduct absorption and emission. While in agreement with the earlier results of Jaaniso [Proc. Est. Acad. Sci., Phys., Math. 34, 277 (1985)] and Fünfschilling et al. [J. Lumin. 36, 85 (1986)], the derived formulas differ substantially from functions used recently [e.g., M. Rätsep et al., Chem. Phys. Lett. 479, 140 (2009)] to model ΔFLN spectra. In contrast to traditional FLN spectra, it is demonstrated that for most physically reasonable parameters, the ΔFLN spectrum reduces simply to the single-site fluorescence lineshape function. These results imply that direct measurement of a bulk-averaged single-site fluorescence lineshape function can be accomplished with no complicated extraction process or knowledge of any additional parameters such as site distribution function shape and width. We argue that previous analysis of ΔFLN spectra obtained for many photosynthetic complexes led to strong artificial lowering of apparent electron-phonon coupling strength, especially on the high-energy side of the pigment site distribution function.

  17. Uncertainty analysis for absorption and first-derivative EPR spectra.

    PubMed

    Tseitlin, Mark; Eaton, Sandra S; Eaton, Gareth R

    2012-11-01

    Electron paramagnetic resonance (EPR) experimental techniques produce absorption or first-derivative spectra. Uncertainty analysis provides the basis for comparison of spectra obtained by different methods. In this study it was used to derive analytical equations to relate uncertainties for integrated intensity and line widths obtained from absorption or first-derivative spectra to the signal-to-noise ratio (SNR), with the assumption of white noise. Predicted uncertainties for integrated intensities and line widths are in good agreement with Monte Carlo calculations for Lorentzian and Gaussian lineshapes. Conservative low-pass filtering changes the noise spectrum, which can be modeled in the Monte Carlo simulations. When noise is close to white, the analytical equations provide useful estimates of uncertainties. For example, for a Lorentzian line with white noise, the uncertainty in the number of spins obtained from the first-derivative spectrum is 2.6 times greater than from the absorption spectrum at the same SNR. Uncertainties in line widths obtained from absorption and first-derivative spectra are similar. The impact of integration or differentiation on SNR and on uncertainties in fitting parameters was analyzed. Although integration of the first-derivative spectrum improves the apparent smoothness of the spectrum, it also changes the frequency distribution of the noise. If the lineshape of the signal is known, the integrated intensity can be determined more accurately by fitting the first-derivative spectrum than by first integrating and then fitting the absorption spectrum. Uncertainties in integrated intensities and line widths are less when the parameters are determined from the original data than from spectra that have been either integrated or differentiated.

  18. Effect of solvents on the fluorescence spectra of bacterial luciferase

    NASA Astrophysics Data System (ADS)

    Sukovataya, Irina E.; Tyulkova, Natalya A.; Kaykova, Elisaveta V.

    2006-08-01

    Bacteria luciferases catalyze the oxidation reaction of the long-chain aliphatic aldehyde and reduced flavinmononucleotide involving molecular oxygen to a respective fatty acid emitting light quanta in the visible spectrum. Fluorescence emission of luciferases from Photobacterium leiognathi dissolved in organic solvent-water mixtures was investigated. Methanol, acetone, dimethyl sulfoxide and formamide were used as organic solvents. As the methanol and acetone concentration is increased the emission maximum peak is decrease. In contrast, with dimethyl sulfoxide and formamide addition induced a increasing of the emission maximum intensity. The values of wavelength maximum (λ max) at the addition of this solvent can shows the spectra shifted to the red by about 12 nm. These increasing in the fluorescence intensity and in the λ max may be due to luciferase denaturation, resulting from the more intensive contact of chromospheres of luciferase with the solvent. At all used concentrations of methanol, acetone and formamide the shape of the fluorescence spectra was not changed. These studies demonstrate that the luciferase tryptophan fluorescence is sensitive to changes of physical-chemical property of enzyme environment. A comparison of activation/inactivation and fluorescence spectra of luciferase in methanol or acetone solutions shows that the extent of inactivation is larger than the extent of fluorescence changes at the same methanol or acetone concentration.

  19. Dipole moment of benzonitrile in its excited S 1 state from thermochromic shifts of fluorescence spectra

    NASA Astrophysics Data System (ADS)

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

    2006-02-01

    The effect of temperature T ranging from 293 to 393 K on absorption and fluorescence spectra of benzonitrile (BN) in ethyl acetate is studied. The absorption spectra of BN remain unchanged with increasing T. The analysis of fluorescence band shift by the Bilot and Kawski theory [L. Bilot, A. Kawski, Z. Naturforsch. 17a (1962) 621], for the known dipole moment value in the ground state μg = 4.18 D and α/ a3 = 0.5 ( α is the polarizability and a is the Onsager interaction radius of the solute), yield the average value of excited state dipole moment μe = 4.42 D. This value is in satisfactory agreement with 4.45, 4.51 and 4.57 D obtained previously from the Stark shift of rotational lines.

  20. The absorption spectra of carbonates and their precursors.

    NASA Astrophysics Data System (ADS)

    Koike, C.; Chihara, H.; Suto, H.

    The carbonates calcite and dolomite have been discovered in the dust shells of evolved stars (Kemper et al. 2002) and young proto stars (Ceccarelli et al. 2002). The mechanism for carbonate formation with a aqueous or non-aqueous process were discussed in their papers. These processes have not yet been reproduced in a laboratory experiment. First of all, we measured the mass absorption spectra of varous carbonates were measured in the mid- and far-infrared region. These spectra show very strong and broad peaks in the far-infrared region. The calcite and dolomite have peaks at about 92 microns and 63 microns, respectively. The alternative process of carbonates has not yet been clear. We investigate the alternative process measuring the spectra of the precursors of carbonates. We will report the preliminary results and discuss about the alternative process comparing the measured spectra of the precursors with the observation.

  1. High Resolution Spectra of Low Redshift Damped Lyalpha Absorption Systems

    NASA Astrophysics Data System (ADS)

    Cohen, R. D.; Beaver, E. A.; Junkkarinen, V. T.; Lyons, R. W.; Smith, H. E.

    1998-05-01

    We have been able to form a fairly complete picture of the galaxy responsible for the z_a=0.395 absorption line system in PKS 1229--021 by combining Keck HIRES and LRIS spectroscopy with observations taken with the Hubble Space Telescope. The image of the absorber is consistent with the inclined disk of a moderately luminous spiral galaxy. We have not been able to detect the continuum from this galaxy spectroscopically, but our LRIS spectra show emission from [O II] lambda3727 which can be interpreted to be indicative of star formation at the rate of a few M_⊙ per year. The HIRES spectra clearly show an ``edge--leading'' absorption profile. Prochaska and Wolfe have predicted that the velocity of the center of mass of the absorbing galaxy should fall near one edge of the absorption profile if the damped Lyalpha systems are due to the rotating disks of spiral galaxies. The [O II] emission velocity is consistent with this, but there is some ambiguity due to the doublet nature of the [O II] emission. Although the absorption lines of the abundant elements are saturated in the components which correspond to the H I absorption, we have been able to measure accurate column densities for Ca II, Ti II, and Mn II for comparison with the H I column density determined from low resolution HST/FOS spectra. The abundances are compatible with approximately 0.1 of solar, with little or no dust, but they are also consistent with lines of sight toward zeta Oph through warm interstellar clouds. HIRES observations of the z_a=0.692 absorption line system in 3CR 286 will also be discussed, after the data are fully analyzed. This work is part of the Goddard High Resolution Spectrograph Guaranteed Time Observations and is supported by NASA grant NAG5--1858 and the NSF.

  2. APM Z >=4 QSO Survey: Spectra and Intervening Absorption Systems

    NASA Astrophysics Data System (ADS)

    Storrie-Lombardi, L. J.; McMahon, R. G.; Irwin, M. J.; Hazard, C.

    1996-09-01

    The APM multicolor survey for bright z > 4 objects, covering 2500 deg^2^ of sky to m_r_ ~ 19, resulted in the discovery of 31 quasars with z ~> 4. High signal-to-noise optical spectrophotometry at 5 A resolution has been obtained for the 28 quasars easily accessible from the northern hemisphere. These spectra have been surveyed to create new samples of high-redshift Lyman-limit systems, damped Lyα absorbers, and metal absorption systems (e.g., C IV and Mg II). In this paper we present the spectra, together with line lists of the detected absorption systems. The QSOs display a wide variety of emission- and absorption-line characteristics, with five exhibiting broad absorption lines and one with extremely strong emission lines (BR 2248 - 1242). Eleven candidate damped Lyα absorption systems have been identified covering the redshift range 2.8 <= z <= 4.4 (eight with z > 3.5). An analysis of the measured redshifts of the high-ionization emission lines with the low-ionization lines shows them to be blueshifted by 430 +/- 60 km s^-1^. In a previous paper (by Storrie-Lombardi et al.) we discussed the redshift evolution of the Lyman limit systems cataloged here. In subsequent papers we will discuss the properties of the Lyα forest absorbers and the redshift and column density evolution of the damped Lyα absorbers.

  3. 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.

  4. Excitation dynamics in Phycoerythrin 545: modeling of steady-state spectra and transient absorption with modified Redfield theory.

    PubMed

    Novoderezhkin, Vladimir I; Doust, Alexander B; Curutchet, Carles; Scholes, Gregory D; van Grondelle, Rienk

    2010-07-21

    We model the spectra and excitation dynamics in the phycobiliprotein antenna complex PE545 isolated from the unicellular photosynthetic cryptophyte algae Rhodomonas CS24. The excitonic couplings between the eight bilins are calculated using the CIS/6-31G method. The site energies are extracted from a simultaneous fit of the absorption, circular dichroism, fluorescence, and excitation anisotropy spectra together with the transient absorption kinetics using the modified Redfield approach. Quantitative fit of the data enables us to assign the eight exciton components of the spectra and build up the energy transfer picture including pathways and timescales of energy relaxation, thus allowing a visualization of excitation dynamics within the complex.

  5. 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.

  6. 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.

  7. Implications for High Energy Blazar Spectra from Intergalactic Absorption Calculations

    NASA Technical Reports Server (NTRS)

    Stecker, F

    2008-01-01

    Given a knowledge of the density spectra intergalactic low energy photons as a function of redshift, one can derive the intrinsic gamma-ray spectra and luminosities of blazars over a range of redshifts and look for possible trends in blazar evolution. Stecker, Baring & Summerlin have found some evidence hinting that TeV blazars with harder spectra have higher intrinsic TeV gamma-ray luminosities and indicating that there may be a correlation of spectral hardness and luminosity with redshift. Further work along these lines, treating recent observations of the blazers lES02291+200 and 3C279 in the TeV and sub-TeV energy ranges, has recently been explored by Stecker & Scully. GLAST will observe and investigate many blazars in the GeV energy range and will be sensitive to blazers at higher redshifts. I examine the implications high redshift gamma-ray absorption for both theoretical and observational blazer studies.

  8. Oscillator strength measurements of atomic absorption lines from stellar spectra

    NASA Astrophysics Data System (ADS)

    Lobel, Alex

    2011-05-01

    Herein we develop a new method to determine oscillator strength values of atomic absorption lines with state-of-the-art detailed spectral synthesis calculations of the optical spectrum of the Sun and of standard spectral reference stars. We update the log(gf) values of 911 neutral lines observed in the KPNO-FTS flux spectrum of the Sun and high-resolution echelle spectra (R = 80 000) of Procyon (F5 IV-V) and Eps Eri (K2 V) observed with large signal-to-noise (S/N) ratios of 2000 using the new Mercator-Hermes spectrograph at La Palma Observatory (Spain). We find for 483 Fe I, 85 Ni I, and 51 Si I absorption lines in the sample a systematic overestimation of the literature log(gf) values with central line depths below 15%. We employ a curve-of-growth analysis technique to test the accuracy of the new oscillator strength values and compare calculated equivalent line widths to the Moore, Minnaert, and Houtgast atlas of the Sun. The online SpectroWeb database at http://spectra.freeshell.org interactively displays the observed and synthetic spectra and provides the new log(gf) values together with important atomic line data. The graphical database is under development for stellar reference spectra of every spectral sub-class observed with large spectral resolution and S/N ratios.

  9. 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.

  10. Analyzing absorption and scattering spectra of micro-scale structures with spectroscopic optical coherence tomography.

    PubMed

    Yi, Ji; Gong, Jianmin; Li, Xu

    2009-07-20

    We demonstrate the feasibility of characterizing the absorption and scattering spectra of micron-scale structures in a turbid medium using a spectroscopic optical coherence tomography (SOCT) system with a bandwidth of 430-650 nm. SOCT measurements are taken from phantoms composed of fluorescent microspheres. The absorption and scattering spectra are recovered with proper selections of spatial window width in the post processing step. Furthermore, we present an analysis using numerical OCT simulation based on full-wave solutions of the Maxwell's Equation to elucidate the origination of the multiple peaks in the OCT image for a single microsphere. Finally, we demonstrate the possibility of identifying contrast agents concentrated in micron-sized scale in an SOCT image. Two different types of microspheres in gel phantom are discriminated based on their distinguished absorbent feature.

  11. 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.

  12. 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.

  13. Discrete electronic-vibrational fluorescence spectra in the low-pressure phenanthrene and naphthacene vapors

    SciTech Connect

    Mirumyants, S.O.; Kozlov, V.K.; Vandyukov, E.A.

    1986-10-01

    In recent years considerable attention has been paid to developing methods for analysis and control of air pollutants. In this work the results of the study on quasiline fluorescence spectra for phenathrene and naphthacene in the gas phase are presented. Despite the fact that phenanthrene is a stereoisomer of anthracene, the shapes and intensities of their absorption and fluorescence spectra are markedly different. The oscillator strength of the first electronic transition in anthracene vapors is 50 times larger than that for the phenanthrene vapor (0.1 and 0.002, respectively). Therefore, the studies of the quasiline fluorescence spectrum of the phenanthrene vapor required a long exposition period (from 7 to 31 h) during the photographic detection. It is known that phenanthrene exhibits a characteristic quasiline spectrum in the 34584000-A range in frozen solutions. The authors have also investigated the possibility of obtaining structured quasiline vapor spectra for a more complex aromatic compound such as naphthacene which comprises four benzyl rings. In conclusion, the quasiline fluorescence spectra for phenanthrene and naphthacene in the gas phase have been obtained for the first time. In certain experimental conditions, phenanthrene and naphthacene emit wellresolved quasiline spectra which are dependent on the excitation frequency, temperature, and vapor pressure. For both compounds there is a frequency range for quasiline fluorescence excitation for which a shift of the quasiline spectrum occurs if the excitation frequency is changed within that range. Also more accurate values for the frequencies of the O-O electronic transition in phenanthrene and naphthacene have been obtained. Diagrams are included.

  14. Interpretation of fluorescence correlation spectra of biopolymer solutions.

    PubMed

    Phillies, George D J

    2016-05-01

    Fluorescence correlation spectroscopy (FCS) is regularly used to study diffusion in non-dilute "crowded" biopolymer solutions, including the interior of living cells. For fluorophores in dilute solution, the relationship between the FCS spectrum G(t) and the diffusion coefficient D is well-established. However, the dilute-solution relationship between G(t) and D has sometimes been used to interpret FCS spectra of fluorophores in non-dilute solutions. Unfortunately, the relationship used to interpret FCS spectra in dilute solutions relies on an assumption that is not always correct in non-dilute solutions. This paper obtains the correct form for interpreting FCS spectra of non-dilute solutions, writing G(t) in terms of the statistical properties of the fluorophore motions. Approaches for applying this form are discussed.

  15. 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.

  16. Optical Absorption Spectra of Hydrous Wadsleyite to 32 GPa

    NASA Astrophysics Data System (ADS)

    Thomas, S.; Goncharov, A. F.; Jacobsen, S. D.; Bina, C. R.; Frost, D. J.

    2009-05-01

    Optical absorption spectra of high-pressure minerals can be used as indirect tools to calculate radiative conductivity of the Earth's interior [e.g., 1]. Recent high-pressure studies show that e.g. ringwoodite, γ-(Mg,Fe)2SiO4, does not become opaque in the near infrared and visible region, as previously assumed, but remains transparent to 21.5 GPa [2]. Therefore, it has been concluded that radiative heat transfer does not necessarily become blocked at high pressures of the mantle and ferromagnesian minerals actually could contribute to the heat flow in the Earth's interior [2]. In this study we use gem-quality single-crystals of hydrous Fe-bearing wadsleyite, β-(Mg,Fe)2SiO4, that were synthesized at 18 GPa and 1400 °C in a multianvil apparatus. Crystals were analyzed by Mössbauer and Raman spectroscopy, electron microprobe analysis and single-crystal X-ray diffraction. For absorption measurements a double-polished 50 μm sized single-crystal of wadsleyite was loaded in a diamond-anvil cell with neon as pressure medium. Optical absorption spectra were recorded at ambient conditions as well as up to 32 GPa from 400 to 50000 cm-1. At ambient pressure the absorption spectrum reveals two broad bands at - 10000 cm-1 and -15000 cm-1, and an absorption edge in the visible-ultraviolet range. With increasing pressure the absorption spectrum changes, both bands continuously shift to higher frequencies as has been observed for ringwoodite [2], but is contrary to earlier presumptions for wadsleyite [3]. Here, we will discuss band assignment along with the influence of iron, compare our results to previous absorption studies of mantle materials [2], and analyze possible implications for radiative conductivity of the transition zone. References: [1] Goncharov et al. (2008), McGraw Yearbook Sci. Tech., 242-245. [2] Keppler & Smyth (2005), Am. Mineral., 90 1209-1212. [3] Ross (1997), Phys. Chem. Earth, 22 113-118.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. Two-photon absorption properties of fluorescent proteins

    PubMed Central

    Drobizhev, Mikhail; Makarov, Nikolay S.; Tillo, Shane E.; Hughes, Thomas E.; Rebane, Aleksander

    2016-01-01

    Two-photon excitation of fluorescent proteins is an attractive approach for imaging living systems. Today researchers are eager to know which proteins are the brightest, and what the best excitation wavelengths are. Here we review the two-photon absorption properties of a wide variety of fluorescent proteins, including new far-red variants, to produce a comprehensive guide to choosing the right FP and excitation wavelength for two-photon applications. PMID:21527931

  4. 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.

  5. The manifestation of optical centers in UV-Vis absorption and luminescence spectra of white blood human cells

    NASA Astrophysics Data System (ADS)

    Terent'yeva, Yu G.; Yashchuk, V. M.; Zaika, L. A.; Snitserova, O. M.; Losytsky, M. Yu

    2016-12-01

    A white blood human cells spectral investigation is presented. The aim of this series of experiments was to obtain and analyze the absorption and luminescence (fluorescence and phosphorescence) spectra at room temperature and at 78 K of newly isolated white blood human cells and their organelles. As a result the optical centers and possible biochemical components that form the studied spectra where identified. Also the differences between the spectra of abnormal cells (B-cell chronic lymphocytic leukemia BCLL) and normal ones were studied for the whole cells and individual organelles.

  6. Interactions of hypericin with a model mutagen - Acridine orange analyzed by light absorption and fluorescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Pietrzak, Monika; Szabelski, Mariusz; Kasparek, Adam; Wieczorek, Zbigniew

    2017-02-01

    The present study was designed to estimate the ability of hypericin to interact with a model mutagen - acridine orange. The hetero-association of hypericin and acridine orange was investigated with absorption and fluorescence spectroscopy methods in aqueous solution of DMSO. The data indicate that hypericin forms complexes with acridine orange and that the association constants are relatively high and depend on DMSO concentration. The absorption spectra of the hypericin - acridine orange complexes were examined as well. Owing to its ability to interact with flat aromatic compounds, hypericin may potentially be used as an interceptor molecule.

  7. UV absorption and fluorescence properties of gas-phase p-difluorobenzene

    NASA Astrophysics Data System (ADS)

    Benzler, Thorsten; Dreier, Thomas; Schulz, Christof

    2017-01-01

    1,4-Difluorobenzene ( p-DFB) is a promising aromatic tracer for determining concentration, temperature, and O2 partial pressure in mixing gas flows based on laser-induced fluorescence (LIF). Signal quantification requires the knowledge of absorption and fluorescence properties as a function of environmental conditions. We report absorption and fluorescence spectra as well as fluorescence lifetimes of p-DFB in the temperature, pressure, and oxygen partial pressure range that is relevant for many applications including internal combustion engines. The UV absorption cross section, investigated between 296 and 675 K, has a peak value close to 266 nm and decreases with temperature, while still exceeding other single-ring aromatics. Time-resolved fluorescence spectra were recorded after picosecond laser excitation at 266 nm as a function of temperature (296-1180 K), pressure (1-10 bar), and O2 partial pressure (0-210 mbar) using a streak camera (temporal resolution 50 ps) coupled to a spectrometer. The fluorescence spectra red-shift ( 2 nm/100 K) and broaden (increase in full width at half maximum by 58% in the investigated temperature range) with temperature. In N2 as bath gas (1 bar), the fluorescence lifetime τ eff decreases with temperature by a factor of about 20 (from 7 ns at 298 K down to 0.32 ns at 1180 K), while at 8 bar the shortest lifetime at 975 K is 0.4 ns. A noticeable pressure dependence (i.e., reduced τ eff) is only visible at 675 K and above. Quenching of p-DFB LIF by O2 (for partial pressures up to 210 mbar) shortens the fluorescence lifetime significantly at room temperature (by a factor of 8), but much less at higher temperatures (by a factor of 1.8 at 970 K). For fixed O2 partial pressures (52 mbar and above), τ eff shows a plateau region with temperature which shifts toward higher temperatures at the higher O2 partial pressures. O2 quenching is less prominent for p-DFB compared to other aromatic compounds investigated so far. The temperature

  8. Accelerated Monte Carlo models to simulate fluorescence spectra from layered tissues.

    PubMed

    Swartling, Johannes; Pifferi, Antonio; Enejder, Annika M K; Andersson-Engels, Stefan

    2003-04-01

    Two efficient Monte Carlo models are described, facilitating predictions of complete time-resolved fluorescence spectra from a light-scattering and light-absorbing medium. These are compared with a third, conventional fluorescence Monte Carlo model in terms of accuracy, signal-to-noise statistics, and simulation time. The improved computation efficiency is achieved by means of a convolution technique, justified by the symmetry of the problem. Furthermore, the reciprocity principle for photon paths, employed in one of the accelerated models, is shown to simplify the computations of the distribution of the emitted fluorescence drastically. A so-called white Monte Carlo approach is finally suggested for efficient simulations of one excitation wavelength combined with a wide range of emission wavelengths. The fluorescence is simulated in a purely scattering medium, and the absorption properties are instead taken into account analytically afterward. This approach is applicable to the conventional model as well as to the two accelerated models. Essentially the same absolute values for the fluorescence integrated over the emitting surface and time are obtained for the three models within the accuracy of the simulations. The time-resolved and spatially resolved fluorescence exhibits a slight overestimation at short delay times close to the source corresponding to approximately two grid elements for the accelerated models, as a result of the discretization and the convolution. The improved efficiency is most prominent for the reverse-emission accelerated model, for which the simulation time can be reduced by up to two orders of magnitude.

  9. Qualitative Analysis of Liquid Hydrocarbon Mixtures by Absorption Spectra of Their Vapors

    NASA Astrophysics Data System (ADS)

    Vesnin, V. L.

    2016-11-01

    Absorption spectra of saturated vapors of hydrocarbons and their mixtures were studied near their first overtones. Absorption spectra of hydrocarbons in the liquid and vapor states were compared. The ability to analyze qualitatively the compositions of liquid hydrocarbon mixtures using absorption spectra of their vapors was demonstrated. Indirect evidence suggested that the nonlinear absorption as a function of concentration that was seen in liquid hydrocarbon mixtures was negligible in their vapors.

  10. 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)…

  11. 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.

  12. Absorption and electroabsorption spectra of carotenoid cation radical and dication

    NASA Astrophysics Data System (ADS)

    Krawczyk, Stanisław

    1998-05-01

    Radical cations and dications of two carotenoids astaxanthin and canthaxanthin were prepared by oxidation with FeCl 3 in fluorinated alcohols at room temperature. Absorption and electroabsorption (Stark effect) spectra were recorded for astaxanthin cations in mixed frozen matrices at temperatures about 160 K. The D 0→D 2 transition in cation radical is at 835 nm. The electroabsorption spectrum for the D 0→D 2 transition exhibits a negative change of molecular polarizability, Δ α=-1.2·10 -38 C·m 2/V (-105 A 3), which seems to originate from the change in bond order alternation in the ground state rather than from the electric field-induced interaction of D 1 and D 2 excited states. Absorption spectrum of astaxanthin dication is located at 715-717 nm, between those of D 0→D 2 in cation radical and S 0→S 2 in neutral carotenoid. Its shape reflects a short vibronic progression and strong inhomogeneous broadening. The polarizability change on electronic excitation, Δ α=2.89·10 -38 C·m 2/V (260 A 3), is five times smaller than in neutral astaxanthin. This value reflects the larger energetic distance from the lowest excited state to the higher excited states than in the neutral molecule.

  13. Excited state absorption spectra and intersystem crossing kinetics in diazanaphthalenes

    NASA Astrophysics Data System (ADS)

    Scott, Gary W.; Talley, Larry D.; Anderson, Robert W.

    1980-05-01

    Picosecond time-resolved, excited state absorption spectra in the visible following excitation at 355 nm are discussed for room temperature solutions of four diazanaphthalenes (DN)—quinoxaline (1,4-DN), quinazoline (1,3-DN), cinnoline (1,2-DN), and phthalazine (2,3-DN). Kinetics of singlet state decay are obtained by monitoring the decay of Sn←S1 bands. The intersystem crossing rate constant (kisc) is found to vary as kisc(1,4-DN)≳kisc(1,3-DN)≳kisc(1,2-DN). The kisc in phthalazine could not be determined from the weak, visible Sn←S1 absorption. Assuming rapid singlet vibrational relaxation and only minor effects due to energy gap variations, these experimental results agree with statistical limit predictions for the relative nonradiative rate. Calculations of the spin-orbit coupling matrix element βel= , using INDO wave functions, give the ordering βel(1,4-DN)≳βel(2,3-DN)≳βel(1,3-DN) ≳βel(1,2-DN).

  14. Transient absorption and luminescence spectra of K9 glass at sub-damage site by ultraviolet laser irradiation

    NASA Astrophysics Data System (ADS)

    Zhang, Z.; Huang, J.; Geng, F.; Zhou, X. Y.; Feng, S. Q.; Cheng, X. L.; Jiang, X. D.; Wu, W. D.; Zheng, W. G.; Tang, Y. J.

    2014-01-01

    Transient absorption and luminescence spectra at sub-damage site of K9 glass by laser irradiation at 355 nm are presented. The dependence of transient absorption on laser energy and number of pulses was investigated. As the energy density increases to 2.54 and 3.18 J/cm2, the transient absorption intensity reaches to about 0.20 range from 400 to 480 nm. With the increase of number of pulses the process of residual absorption appears, which can be used to explain the fatigue effect of K9 glass. The defects in K9 glass were investigated by fluorescence and Raman spectra. The fluorescence band centered at about 410 nm is attributed to oxygen deficiency centers. The mechanism of two-photon ionization plays a critical role at sub-damage site. Compared to the Raman spectra of pristine site, intensity of Raman spectra is very high at a lower energy density, while it decreased at a higher energy density.

  15. Fluorescence and absorption spectroscopy of the weakly fluorescent chlorophyll a in cytochrome b6f of Synechocystis PCC6803.

    PubMed Central

    Peterman, E J; Wenk, S O; Pullerits, T; Pâlsson, L O; van Grondelle, R; Dekker, J P; Rögner, M; van Amerongen, H

    1998-01-01

    A spectroscopic characterization of the chlorophyll a (Chl) molecule in the monomeric cytochrome b6f complex (Cytb6f) isolated from the cyanobacterium Synechocystis PCC6803 is presented. The fluorescence lifetime and quantum yield have been determined, and it is shown that Chl in Cytb6f has an excited-state lifetime that is 20 times smaller than that of Chl in methanol. This shortening of the Chl excited state lifetime is not caused by an increased rate of intersystem crossing. Most probably it is due to quenching by a nearby amino acid. It is suggested that this quenching is a mechanism for preventing the formation of Chl triplets, which can lead to the formation of harmful singlet oxygen. Using site-selected fluorescence spectroscopy, detailed information on vibrational frequencies in both the ground and Qy excited states has been obtained. The vibrational frequencies indicate that the Chl molecule has one axial ligand bound to its central magnesium and accepts a hydrogen bond to its 13(1)-keto carbonyl. The results show that the Chl binds to a well-defined pocket of the protein and experiences several close contacts with nearby amino acids. From the site-selected fluorescence spectra, it is further concluded that the electron-phonon coupling is moderately strong. Simulations of both the site-selected fluorescence spectra and the temperature dependence of absorption and fluorescence spectra are presented. These simulations indicate that the Huang-Rhys factor characterizing the electron-phonon coupling strength is between 0.6 and 0.9. The width of the Gaussian inhomogeneous distribution function is 210 +/- 10 cm-1. PMID:9649396

  16. Molecular iodine fluorescence spectra generated with helium-neon lasers for spectrometer calibration.

    PubMed

    Williamson, J Charles

    2010-12-01

    Gas-phase molecular iodine laser-induced fluorescence (LIF) spectra were recorded out to 815 nm at 1 cm(-1) resolution using green, yellow, and red helium-neon (HeNe) lasers as excitation sources. Nine previously unreported I(2) B←X absorption transitions accessed by these lasers were identified, and specific rovibronic transition assignments were made for two hundred LIF peaks--more than sixty per laser. These I(2) LIF peaks can be used to calibrate the vacuum wavenumber coordinate of spectrometers to better than 0.1 cm(-1) accuracy. In particular, green HeNe excitation of the I(2) R(106) 28-0 transition leads to strong fluorescence well suited for calibration, with a rotational doublet spacing of 15 cm(-1) and a doublet-to-doublet spacing of 190 cm(-1). Calibration by HeNe I(2) LIF may be an especially valuable technique for Raman spectroscopy applications.

  17. Estimation of damped oscillation associated spectra from ultrafast transient absorption spectra.

    PubMed

    van Stokkum, Ivo H M; Jumper, Chanelle C; Snellenburg, Joris J; Scholes, Gregory D; van Grondelle, Rienk; Malý, Pavel

    2016-11-07

    When exciting a complex molecular system with a short optical pulse, all chromophores present in the system can be excited. The resulting superposition of electronically and vibrationally excited states evolves in time, which is monitored with transient absorption spectroscopy. We present a methodology to resolve simultaneously the contributions of the different electronically and vibrationally excited states from the complete data. The evolution of the excited states is described with a superposition of damped oscillations. The amplitude of a damped oscillation cos(ωnt)exp(-γnt) as a function of the detection wavelength constitutes a damped oscillation associated spectrum DOASn(λ) with an accompanying phase characteristic φn(λ). In a case study, the cryptophyte photosynthetic antenna complex PC612 which contains eight bilin chromophores was excited by a broadband optical pulse. Difference absorption spectra from 525 to 715 nm were measured until 1 ns. The population dynamics is described by four lifetimes, with interchromophore equilibration in 0.8 and 7.5 ps. We have resolved 24 DOAS with frequencies between 130 and 1649 cm(-1) and with damping rates between 0.9 and 12 ps(-1). In addition, 11 more DOAS with faster damping rates were necessary to describe the "coherent artefact." The DOAS contains both ground and excited state features. Their interpretation is aided by DOAS analysis of simulated transient absorption signals resulting from stimulated emission and ground state bleach.

  18. Estimation of damped oscillation associated spectra from ultrafast transient absorption spectra

    NASA Astrophysics Data System (ADS)

    van Stokkum, Ivo H. M.; Jumper, Chanelle C.; Snellenburg, Joris J.; Scholes, Gregory D.; van Grondelle, Rienk; Malý, Pavel

    2016-11-01

    When exciting a complex molecular system with a short optical pulse, all chromophores present in the system can be excited. The resulting superposition of electronically and vibrationally excited states evolves in time, which is monitored with transient absorption spectroscopy. We present a methodology to resolve simultaneously the contributions of the different electronically and vibrationally excited states from the complete data. The evolution of the excited states is described with a superposition of damped oscillations. The amplitude of a damped oscillation cos(ωnt)exp(-γnt) as a function of the detection wavelength constitutes a damped oscillation associated spectrum DOASn(λ) with an accompanying phase characteristic φn(λ). In a case study, the cryptophyte photosynthetic antenna complex PC612 which contains eight bilin chromophores was excited by a broadband optical pulse. Difference absorption spectra from 525 to 715 nm were measured until 1 ns. The population dynamics is described by four lifetimes, with interchromophore equilibration in 0.8 and 7.5 ps. We have resolved 24 DOAS with frequencies between 130 and 1649 cm-1 and with damping rates between 0.9 and 12 ps-1. In addition, 11 more DOAS with faster damping rates were necessary to describe the "coherent artefact." The DOAS contains both ground and excited state features. Their interpretation is aided by DOAS analysis of simulated transient absorption signals resulting from stimulated emission and ground state bleach.

  19. Solvatochromic Shifts on Absorption and Fluorescence Bands of N,N-Dimethylaniline.

    PubMed

    Fdez Galván, Ignacio; Elena Martín, M; Muñoz-Losa, Aurora; Aguilar, Manuel A

    2009-02-10

    A theoretical study of the absorption and fluorescence UV/vis spectra of N,N-dimethylaniline in different solvents has been performed, using a method combining quantum mechanics, molecular mechanics, and the mean field approximation. The transitions between the three lowest-lying states have been calculated in vacuum as well as in cyclohexane, tetrahydrofuran, and water. The apparent anomalies experimentally found in water (a blue shift in the absorption bands with respect to the trend in other solvents, and an abnormally high red shift for the fluorescence band) are well reproduced and explained in view of the electronic structure of the solute and the solvent distribution around it. Additional calculations were done with a mixture of cyclohexane and tetrahydrofuran as solvent, which displays a nonlinear solvatochromic shift. Results, although not conclusive, are consistent with experiment and provide a possible explanation for the nonlinear behavior in the solvent mixture.

  20. 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.

  1. A fluorescent benzothiazole probe with efficient two-photon absorption

    NASA Astrophysics Data System (ADS)

    Echevarria, Lorenzo; Moreno, Iván; Camacho, José; Salazar, Mary Carmen; Hernández, Antonio

    2012-11-01

    In this work, we report the two-photon absorption of 2-[4-(dimethylamino)phenyl]-1,3-benzothiazole-6-carbonitrile (DBC) in DMSO solution pumping at 779 nm with a 10 ns pulse laser-Nd:YAG system. The obtained two-photon absorption cross-section in DBC (407 ± 18 GM) is considerably high. Because DBC is a novel compound and have high values of fluorescence quantum yield, this result is expected to have an impact in biomolecules detection, diagnosis and treatment of cancer. Similar structures have previously been reported to show remarkable antitumour effects.

  2. Quantitative fluorescence spectroscopy in turbid media: a practical solution to the problem of scattering and absorption.

    PubMed

    Chen, Yao; Chen, Zeng-Ping; Yang, Jing; Jin, Jing-Wen; Zhang, Juan; Yu, Ru-Qin

    2013-02-19

    The presence of practically unavoidable scatterers and background absorbers in turbid media such as biological tissue or cell suspensions can significantly distort the shape and intensity of fluorescence spectra of fluorophores and, hence, greatly hinder the in situ quantitative determination of fluorophores in turbid media. In this contribution, a quantitative fluorescence model (QFM) was proposed to explicitly model the effects of the scattering and absorption on fluorescence measurements. On the basis of the proposed model, a calibration strategy was developed to remove the detrimental effects of scattering and absorption and, hence, realize accurate quantitative analysis of fluorophores in turbid media. A proof-of-concept model system, the determination of free Ca(2+) in turbid media using Fura-2, was utilized to evaluate the performance of the proposed method. Experimental results showed that QFM can provide quite precise concentration predictions for free Ca(2+) in turbid media with an average relative error of about 7%, probably the best results ever achieved for turbid media without the use of advanced optical technologies. QFM has not only good performance but also simplicity of implementation. It does not require characterization of the light scattering properties of turbid media, provided that the light scattering and absorption properties of the test samples are reasonably close to those of the calibration samples. QFM can be developed and extended in many application areas such as ratiometric fluorescent sensors for quantitative live cell imaging.

  3. 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.

  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. 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

  6. 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.

  7. 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

  8. 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.

  9. [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.

  10. Influence of transannular interaction over absorption and fluorescent properties of [2.2] paracyclophane and its phenyl derivatives

    NASA Astrophysics Data System (ADS)

    Nurmukhametov, R. N.; Shapovalov, A. V.; Antonov, D. Yu.

    2016-12-01

    A significant bathochromic shift of the fluorescent and long-wavelength absorption bands of [2.2] paracyclophane comparing to corresponding bands of alkyl-benzenes is due to a strong transannular interaction, resulting in formation of a principally new excited state of lower energy. It is concluded that the fluorescent levels for alkylbenzene excimers and for the macrocycle are of the same nature. Analysis of [2.2] paracyclophane mono- and diphenylderivatives spectra shows that their intensive absorption bands (230-310 nm) are originated from electron transitions of biphenyl groups and weak long wavelength absorption (310-340 nm) and fluorescent bands are governed by the same electron transitions between ground and excimer-like excited states as in the case of non-substituted macrocycle.

  11. [Absorption spectra of nucleic acids and related compounds in the spectral region 120--280 nm].

    PubMed

    Kiseleva, M N; Zarochentseva, E P; Dodonova, N Ia

    1975-01-01

    The absorption spectra of thin films of nucleic acids, nucleosides, nucleotides, D-ribose, Na3PO4 in vacuum ultraviolet region are measured. In the spectral region 280--160 nm the absorption spectra consist of the bands of nucleic acid bases. In the range shorter than 160 nm the absorption is determined by phosphate and D-ribose groups. The methods of thin films preparation are discussed.

  12. A QM/MM study of absorption spectra of uracil derivatives in aqueous solution

    NASA Astrophysics Data System (ADS)

    Nakayama, Akira

    2016-12-01

    The absorption spectra of three representative uracil derivatives (uracil, thymine, and 5-fluorouracil) in aqueous solution are investigated by the QM/MM approach, where the CASPT2 method is employed to evaluate the excitation energies. The computed absorption spectra are in good agreement with the experimental results, and in particular, the relative values of the absorption maximum between these derivatives are well reproduced in the simulations.

  13. Studies of OH - absorption and optical absorption spectra in LiNbO 3 : Mg, Ti crystals

    NASA Astrophysics Data System (ADS)

    Liu, Jianjun; Zhang, Wanlin; Zhang, Guangyin

    1996-02-01

    The OH - absorption spectra and the UV absorption edges of LiNbO 3 : Mg, Ti crystals have been measured. It is shown that Ti doping raises the Mg doping threshold level, and shifts the absorption edge towards longer wavelengths. The results can be explained by the formation of Mg Li2+Ti Nb4+ pairs after all antisite defects Nb Li have been replaced.

  14. 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

  15. 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.

  16. Specific features of Tm 3+ doped BiB 3O 6 glasses fluorescence spectra and their kinetics

    NASA Astrophysics Data System (ADS)

    Majchrowski, A.; Jaroszewicz, L.; Kuznik, W.; Brik, M. G.; Klosowicz, S.; Kityk, I. V.

    2012-02-01

    Synthesis and spectral fluorescent features of the thulium-doped BiB 3O 6 glasses are presented. All spectra were recorded using a pulsed (pulse energy ca. 1 μJ, pulse duration 10 ns) 355 nm third harmonic of 10 kHz Nd:YAG laser as an excitation source. A laser beam was focused in a backscattering geometry onto about 1 mm 2 spot on the surface of a sample. The Andor SR-303 i spectrograph equipped with an Andor DH-501 intensified charge coupled device with spectral resolution up to 1 nm was used as a spectra recorder. The time-resolution of this system can be as low as 5 ns. The decay kinetics was derived from integrated time-resolved spectra. Additionally the absorption and excitation spectra were measured. The main parameters of the Judd-Ofelt analysis were calculated and comparison of the obtained results with corresponding data for other materials was carried out.

  17. Specific features of Tm3+ doped BiB3O6 glasses fluorescence spectra and their kinetics.

    PubMed

    Majchrowski, A; Jaroszewicz, L; Kuznik, W; Brik, M G; Klosowicz, S; Kityk, I V

    2012-02-15

    Synthesis and spectral fluorescent features of the thulium-doped BiB(3)O(6) glasses are presented. All spectra were recorded using a pulsed (pulse energy ca. 1μJ, pulse duration 10ns) 355nm third harmonic of 10kHz Nd:YAG laser as an excitation source. A laser beam was focused in a backscattering geometry onto about 1mm(2) spot on the surface of a sample. The Andor SR-303i spectrograph equipped with an Andor DH-501 intensified charge coupled device with spectral resolution up to 1nm was used as a spectra recorder. The time-resolution of this system can be as low as 5ns. The decay kinetics was derived from integrated time-resolved spectra. Additionally the absorption and excitation spectra were measured. The main parameters of the Judd-Ofelt analysis were calculated and comparison of the obtained results with corresponding data for other materials was carried out.

  18. Influence of substitution on the T-T absorption spectra in furocoumarins

    NASA Astrophysics Data System (ADS)

    Bryantseva, N. G.

    2006-11-01

    The present paper deals with compounds called photosensitizers, namely, psoralen, 3,4-phenyl-4',5'- cyclohexylpsoralen, 4'-methyl-3,4-cycloheptyl psoralen, 4',5'-dimethyl-3,4-cyclohexyl psoralen (fig. 1). The absorption spectra from excited triplets states were investigated. The computed triplet-triplet absorption spectra of research compounds have been determined using INDO method. The experimental triplet-triplet absorption spectra have been obtained using the technique of laser flash photolysis in ethanol. The compare of computed and experimental data is shows that the computed second band wavelenght throughout agree very well (0,5-6 nm) with experimental data.

  19. 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.

  20. [Terahertz Absorption Spectra Simulation of Glutamine Based on Quantum-Chemical Calculation].

    PubMed

    Zhang, Tian-yao; Zhang, Zhao-hui; Zhao, Xiao-yan; Zhang, Han; Yan, Fang; Qian, Ping

    2015-08-01

    With simulation of absorption spectra in THz region based on quantum-chemical calculation, the THz absorption features of target materials can be assigned with theoretical normal vibration modes. This is necessary for deeply understanding the origin of THz absorption spectra. The reliabilities of simulation results mainly depend on the initial structures and theoretical methods used throughout the calculation. In our study, we utilized THz-TDS to obtain the THz absorption spectrum of solid-state L-glutamine. Then three quantum-chemical calculation schemes with different initial structures commonly used in previous studies were proposed to study the inter-molecular interactions' contribution to the THz absorption of glutamine, containing monomer structure, dimer structure and crystal unit cell structure. After structure optimization and vibration modes' calculation based on density functional theory, the calculation results were converted to absorption spectra by Lorentzian line shape function for visual comparison with experimental spectra. The result of dimmer structure is better than monomer structure in number of absorption features while worse than crystal unit cell structure in position of absorption peaks. With the most reliable simulation result from crystal unit cell calculation, we successfully assigned all three experimental absorption peaks of glutamine ranged from 0.3 to 2.6 THz with overall vibration modes. Our study reveals that the crystal unit cell should be used as initial structure during theoretical simulation of solid-state samples' THz absorption spectrum which comprehensively considers not only the intra-molecular interactions but also inter-molecular interactions.

  1. 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.

  2. Application of the Kubelka-Munk correction for self-absorption of fluorescence emission in carmine lake paint layers.

    PubMed

    Clementi, Catia; Miliani, Costanza; Verri, Giovanni; Sotiropoulou, Sophia; Romani, Aldo; Brunetti, Brunetto G; Sgamellotti, A

    2009-12-01

    The variations of the fluorescence emission of carmine lake travelling through an absorbing and scattering medium, such as a paint layer, were investigated by ultraviolet (UV)-visible absorption, fluorescence spectroscopy, and imaging techniques. Samples of the lake were studied in dilute and saturated solutions, on a reference test panel and a real case study. Relevant spectral modifications have been observed as a function of the lake concentration mainly consisting of a fluorescence quenching, red shift of emission maxima, and deformation of emission band. The application of a correction factor based on the Kubelka-Munk model allowed fluorescence spectra obtained in solution and on painted samples of known composition to be compared and correlated, highlighting that the fluorescence of the lake within paint layers is affected by both self-absorption and aggregation phenomena. This approach has been successfully applied on a painting by G. Vasari for the noninvasive identification of carmine lake. The results reported here emphasize the necessity of taking physical phenomena into account in the interpretation of the fluorescence spectra for a proper and reliable characterization and identification of painting materials in works of art.

  3. 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

  4. Absorption and fluorescence of PRODAN in phospholipid bilayers: a combined quantum mechanics and classical molecular dynamics study.

    PubMed

    Cwiklik, Lukasz; Aquino, Adelia J A; Vazdar, Mario; Jurkiewicz, Piotr; Pittner, Jiří; Hof, Martin; Lischka, Hans

    2011-10-20

    Absorption and fluorescence spectra of PRODAN (6-propionyl-2-dimethylaminonaphthalene) were studied by means of the time-dependent density functional theory and the algebraic diagrammatic construction method. The influence of environment, a phosphatidylcholine lipid bilayer and water, was taken into account employing a combination of quantum chemical calculations with empirical force-field molecular dynamics simulations. Additionally, experimental absorption and emission spectra of PRODAN were measured in cyclohexane, water, and lipid vesicles. Both planar and twisted configurations of the first excited state of PRODAN were taken into account. The twisted structure is stabilized in both water and a lipid bilayer, and should be considered as an emitting state in polar environments. Orientation of the excited dye in the lipid bilayer significantly depends on configuration. In the bilayer, the fluorescence spectrum can be regarded as a combination of emission from both planar and twisted structures.

  5. 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.

  6. 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.

  7. TD-DFT Study of Absorption and Emission Spectra of 2-(2'-Aminophenyl)benzothiazole Derivatives in Water.

    PubMed

    Manojai, Natthaporn; Daengngern, Rathawat; Kerdpol, Khanittha; Kungwan, Nawee; Ngaojampa, Chanisorn

    2017-03-01

    Reduction of aromatic azides to amines is an important property of hydrogen sulphide (H2S) which is useful in fluorescence microscopy and H2S probing in cells. The aim of this work is to study the substituent effect on the absorption and emission spectra of 2-(2'-aminophenyl)benzothiazole (APBT) in order to design APBT derivatives for the use of H2S detection. Absorption and emission spectra of APBT derivatives in aqueous environment were calculated using density functional theory (DFT) and time-dependent DFT (TD-DFT) at B3LYP/6-311+G(d,p) level. The computed results favoured the substitution of strong electron-donating group on the phenyl ring opposite to the amino group for their large Stokes' shifts and emission wavelengths of over 600 nm. Also, three designed compounds were suggested as potential candidates for the fluorescent probes. Such generalised guideline learnt from this work can also be useful in further designs of other fluorescent probes of H2S in water.

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

    PubMed

    Grante, Ilze; Actins, Andris; Orola, Liana

    2014-08-14

    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.

  9. Systematic view of optical absorption spectra in the actinide series

    SciTech Connect

    Carnall, W.T.

    1985-01-01

    In recent years sufficient new spectra of actinides in their numerous valence states have been measured to encourage a broader scale analysis effort than was attempted in the past. Theoretical modelling in terms of effective operators has also undergone development. Well established electronic structure parameters for the trivalent actinides are being used as a basis for estimating parameters in other valence states and relationships to atomic spectra are being extended. Recent contributions to our understanding of the spectra of 4+ actinides have been particularly revealing and supportive of a developing general effort to progress beyond a preoccupation with modelling structure to consideration of the much broader area of structure-bonding relationships. We summarize here both the developments in modelling electronic structure and the interpretation of apparent trends in bonding. 60 refs., 9 figs., 1 tab.

  10. 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.

  11. 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.

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

    NASA Astrophysics Data System (ADS)

    Hoepffner, Nicolas; Sathyendranath, Shubha

    1993-12-01

    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.

  13. 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

  14. 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.

  15. 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.

  16. Electronic absorption spectra of blood plasma of patients with various forms of goiter

    NASA Astrophysics Data System (ADS)

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

    2012-01-01

    The results of absorption spectra of blood plasma in the ultraviolet and visible areas of the spectrum using the technique of spherical photometer. Possibilities of using these spectra to detect the diseases - diffuse toxic goiter and nodular euthyroid goiter and to control the surgical treatment of this pathology.

  17. Electronic absorption spectra of blood plasma of patients with various forms of goiter

    NASA Astrophysics Data System (ADS)

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

    2011-09-01

    The results of absorption spectra of blood plasma in the ultraviolet and visible areas of the spectrum using the technique of spherical photometer. Possibilities of using these spectra to detect the diseases - diffuse toxic goiter and nodular euthyroid goiter and to control the surgical treatment of this pathology.

  18. Analysis of absorption and scattering spectra for assessing apple fruit internal quality after harvest and storage

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Optical absorption and scattering properties are useful for quantifying light interaction with plant tissue, as well as for quality assessment of horticultural products. The aim of this research was to measure the absorption and reduced scattering coefficient spectra of two cultivars of apple (Malus...

  19. 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.

  20. 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...

  1. 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

  2. The Extragalactic Background Light and Absorption in Gamma Ray Spectra

    NASA Astrophysics Data System (ADS)

    Gilmore, Rudy C.

    2008-03-01

    Recent state-of-the-art semi-analytic models (SAMs) can now accurately model the history of galaxy formation and evolution. These SAMs utilize a 'forward evolution' approach and include all of the important processes for determining photon emission from galaxies, such as cooling and shock heating of gas, galaxy mergers, star formation and aging, supernova and AGN feedback, and the reprocessing of light by dust. I will be presenting our group's latest prediction of the extra-galactic background light based on this work and will discuss the implications for the attenuation of VHE gamma rays from distant sources due to pair-production. These results will be compared to recent limits placed on the EBL by observations of GeV and TeV blazar spectra by experiments such as H.E.S.S., MAGIC and VERITAS. The implications for reconstructing the intrinsic spectra of distant blazars will be addressed.

  3. On the nitrogen-induced far-infrared absorption spectra

    NASA Technical Reports Server (NTRS)

    Dore, P.; Filabozzi, A.

    1987-01-01

    The rototranslational absorption spectrum of gaseous N2 is analyzed, considering quadrupolar and hexadecapolar induction mechanisms. The available experimental data are accounted for by using a line-shape analysis in which empirical profiles describe the single-line translational profiles. Thus, a simple procedure is derived that allows the prediction of the N2 spectrum at any temperature. On the basis of the results obtained for the pure gas, a procedure to compute the far-infrared spectrum of the N2-Ar gaseous mixture is also proposed. The good agreement between computed and experimental N2-Ar data indicates that it is possible to predict the far-infrared absorption induced by N2 on the isotropic polarizability of any interacting partner.

  4. An iron absorption model of gamma-ray burst spectra

    NASA Technical Reports Server (NTRS)

    Liang, Edison P.; Kargatis, Vincent E.

    1994-01-01

    Most gamma-ray bursts (GRBs) exhibit deficits of X-rays below approximately 200 keV. Here we consider a spectral model in which the burst source is shielded by an optically thick layer of circumburster material (CBM) rich in iron-group elements whose photoelectric absorption opacity exceeds the Thomson opacity below approximately 120 keV. For power-law distributions of absorption depths along the lines of sight the absorbed spectrum can indeed mimic the typial GRB spectrum. This model predicts that (a) the spectrum should evolve monotonically from hard to soft during each energy release, which is observed in most bursts, especially in fast rise exponential decay bursts; (b) Fe spectral features near 7 keV may be present in some bursts; and (c) the ratio of burst distances to the CBM and to Earth should be approximately 10(exp -11) if the spectral evolution is purely due to Fe stripping by the photons.

  5. 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.

  6. 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.

  7. Absorption Spectra of High-Temperature Solid Propellant Flames

    DTIC Science & Technology

    1974-08-01

    emission, was used as the calibration parameter. A Beer -Lambert type plot of the modified absorbance versus the respective specie concentration...the flame. Where P°^ is the incident radiant power at wave- length X, and P^ is the transmitted radiant power at wavelength A. Beer -Lambert type...absorption spectroscopy is based on the use of the Beer -Lambert Law, 103 P? ^n-^-»Kxce , (1) where P*J is the Incident radiant power, P^ is the

  8. 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.

  9. Ab-initio method for X-ray absorption spectra simulation of hydride molecular ions

    NASA Astrophysics Data System (ADS)

    Puglisi, Alessandra; Sisourat, Nicolas; Carniato, Stéphane

    2017-03-01

    Soft X-ray absorption spectra of molecular ions are important data for the modeling and understanding of laboratory and astrophysical plasma. In this work, we present an ab-initio method, based on the Configuration Interaction (CI) approach, for the calculations of energy positions and oscillator strengths of X-ray absorption spectra. Furthermore, we investigate the effects of the choice of the nature and number of spin-orbitals used in the CI expansion on the spectra. The method is applied on three hydride molecular ions, namely CH+, OH+ and SiH+. However, the approach proposed here is general and may thus be applied to any kind of molecular ions.

  10. 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.

  11. [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.

  12. Fluorescence Spectra Of Corneal Tissue Under Excimer Laser Irradiation

    NASA Astrophysics Data System (ADS)

    Loree, Thomas R.; Johnson, Tamara M.; Birmingham, Brian S.; McCord, Roy C.

    1988-06-01

    The corneas of pigs' eyes were irradiated with ablative levels of 193, 248, and 308 nm and the spectra of the produced light recorded. In all cases there was an appreciable amount of uv light produced in the 300-400 nm band. The 193 nm irradiation exhibited a threshold at 0.5 J/cm2; markedly different spectra were produced below and above that threshold.

  13. Electronic structure and TDDFT optical absorption spectra of silver nanorods.

    PubMed

    Johnson, Hannah E; Aikens, Christine M

    2009-04-23

    Density functional theory calculations are employed to determine optimized geometries and excitation spectra for small pentagonal silver nanorods Ag(n), with n = 13, 19, 25, 31, 37, 43, 49, 55, 61, and 67 in various charge states. The asymptotically correct SAOP functional is utilized in the excitation calculations. Silver nanorods exhibit a sharp longitudinal excitation that results from a mixture of orbital transitions; the wavelength for this excitation depends linearly on the length of the nanorod. The broad transverse excitation arises from multiple excited states. A particle-in-a-box model is employed to explain the linear dependence of the longitudinal excitation wavelength on nanorod length.

  14. Carbon dioxide laser absorption spectra of toxic industrial compounds.

    PubMed

    Loper, G L; Sasaki, G R; Stamps, M A

    1982-05-01

    CO(2) laser absorption cross-section data are reported for acrolein, styrene, ethyl acrylate, trichloroethylene, vinyl bromide, and vinylidene chloride. These data indicate that sub parts per billion level, interference-free detection limits should be possible for these compounds by the CO(2) laser photoacoustic technique. Photoacoustic detectabilities below 40 ppb should be possible for these compounds in the presence of ambient air concentrations of water vapor and other anticipated interferences. These compounds are also found not to be important interferences in the detection of toxic hydrazine-based rocket fuels by CO(2) laser spectroscopic techniques.

  15. Femtosecond Transient Absorption Spectra and Relaxation Dynamics of SWNT in SDS Micellar Solutions

    NASA Astrophysics Data System (ADS)

    Nadtochenko, V. A.; Lobach, A. S.; Gostev, F. E.; Tcherbinin, D. O.; Sobennikov, A.; Sarkisov, O. M.

    2005-09-01

    Transient absorption spectra and relaxation dynamics of excited SWNT were studied by femtosecond absorption spectroscopy as a function of: the energy of excitation quanta (ℏω = 2 eV, 2.5 eV, 4 eV); the density of the excitation energy; polarizations of the pump and probe pulses. The transient absorption spectra were monitored by white supercontinuum light pulse in the spectral region of ˜ 1.2 ÷ 3.6 eV. The induced transient absorption spectra of SWNT are considered as filling of the size-quantized energy bands with nonequilibrium carriers; renormalization of the one-dimensional energy bands at high density of the induced plasma; quantum confined Stark effect and screening of excitons. The anisotropic relaxation rate is observed.

  16. In vivo absorption spectra of the two stable states of the Euglena photoreceptor photocycle.

    PubMed

    Barsanti, Laura; Coltelli, Primo; Evangelista, Valtere; Passarelli, Vincenzo; Frassanito, Anna Maria; Vesentini, Nicoletta; Santoro, Fabrizio; Gualtieri, Paolo

    2009-01-01

    Euglena gracilis possesses a simple but sophisticated light detecting system, consisting of an eyespot formed by carotenoids globules and a photoreceptor. The photoreceptor of Euglena is characterized by optical bistability, with two stable states. In order to provide important and discriminating information on the series of structural changes that Euglena photoreceptive protein(s) undergoes inside the photoreceptor in response to light, we measured the in vivo absorption spectra of the two stable states A and B of photoreceptor photocycle. Data were collected using two different devices, i.e. a microspectrophotometer and a digital microscope. Our results show that the photocycle and the absorption spectra of the photoreceptor possess strong spectroscopic similarities with a rhodopsin-like protein. Moreover, the analysis of the absorption spectra of the two stable states of the photoreceptor and the absorption spectrum of the eyespot suggests an intriguing hypothesis for the orientation of microalgae toward light.

  17. 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.

  18. Electronic absorption spectra of hydrogenated protonated naphthalene and proflavine

    NASA Astrophysics Data System (ADS)

    Bonaca, A.; Bilalbegović, G.

    2011-09-01

    We study hydrogenated cations of two polycyclic hydrocarbon molecules as models of hydrogenated organic species that form in the interstellar medium. Optical spectra of the hydrogenated naphthalene cation Hn-C10H+8 for n= 1, 2 and 10, as well as the astrobiologically interesting hydrogenated proflavine cation Hn-C13H11N+3 for n= 1 and 14, are calculated. The pseudopotential time-dependent density functional theory is used. It is found that the fully hydrogenated proflavine cation H14-C13H11N+3 shows a broad spectrum in which the positions of individual lines are almost lost. The positions, shapes and intensities of lines change in hydronaphthalene and hydroproflavine cations, showing that hydrogen additions induce substantially different optical spectra in comparison with base polycyclic hydrocarbon cations. One calculated line in the visible spectrum of H10-C10H+8 and one in the visible spectrum of H-C13H11N+3 are close to the measured diffuse interstellar bands. We also present the positions of near-ultraviolet lines.

  19. 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.

  20. Comparison of absorption, fluorescence, and polarization spectroscopy of atomic rubidium

    NASA Astrophysics Data System (ADS)

    Ashman, Seth; Stifler, Cayla; Romero, Joaquin

    2015-05-01

    An ongoing spectroscopic investigation of atomic rubidium utilizes a two-photon, single-laser excitation process. Transitions accessible with our tunable laser include 5P1 / 2F' <-- 5S1 / 2 F and 5P3 / 2F' <-- 5S1 / 2 F . The laser is split into a pump and probe beam to allow for Doppler-free measurements of transitions between hyperfine levels. The pump and probe beams are overlapped in a counter-propagating geometry and the laser frequency scans over a transition. Absorption, fluorescence and polarization spectroscopy techniques are applied to this basic experimental setup. The temperature of the vapor cell and the power of the pump and probe beams have been varied to explore line broadening effects and signal-to-noise of each technique. This humble setup will hopefully grow into a more robust experimental arrangement in which double resonance, two-laser excitations are used to explore hyperfine state changing collisions between rubidium atoms and noble gas atoms. Rb-noble gas collisions can transfer population between hyperfine levels, such as 5P3 / 2 (F' = 3) <-- Collision 5P3 / 2 (F ' = 2) , and the probe beam couples 7S1 / 2 (F'' = 2) <-- 5P3 / 2 (F' = 3) . Polarization spectroscopy signal depends on the rate of population transfer due to the collision as well as maintaining the orientation created by the pump laser. Fluorescence spectroscopy relies only on transfer of population due to the collision. Comparison of these techniques yields information regarding the change of the magnetic sublevels, mF, during hyperfine state changing collisions.

  1. Linewidths in excitonic absorption spectra of cuprous oxide

    NASA Astrophysics Data System (ADS)

    Schweiner, Frank; Main, Jörg; Wunner, Günter

    2016-02-01

    We present a theoretical calculation of the absorption spectrum of cuprous oxide (Cu2O ) based on the general theory developed by Y. Toyozawa. An inclusion not only of acoustic phonons but also of optical phonons and of specific properties of the excitons in Cu2O like the central-cell corrections for the 1 S exciton allows us to calculate the experimentally observed linewidths in experiments by T. Kazimierczuk et al. [T. Kazimierczuk, D. Fröhlich, S. Scheel, H. Stolz, and M. Bayer, Nature (London) 514, 343 (2014), 10.1038/nature13832] within the same order of magnitude, which demonstrates a clear improvement in comparison to earlier work on this topic. We also discuss a variety of further effects, which explain the still observable discrepancy between theory and experiment but can hardly be included in theoretical calculations.

  2. 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.

  3. 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).

  4. Electric-field-induced changes in absorption and fluorescence of the green fluorescent protein chromophore in a PMMA film.

    PubMed

    Nakabayashi, Takakazu; Hino, Kazuyuki; Ohta, Yuka; Ito, Sayuri; Nakano, Hirofumi; Ohta, Nobuhiro

    2011-07-07

    External electric field effects on absorption, fluorescence, and fluorescence decay of p-HBDI that is a model compound of the chromophore of GFP have been examined in a poly(methyl methacrylate) film. The electroabsorption spectrum is similar in shape to the first derivative of the absorption spectrum, which results from the difference in molecular polarizability between the ground state and the Franck-Condon excited state. The electrophotoluminescence spectrum is dominated by the corresponding fluorescence spectrum, indicating the enhancement of the fluorescence intensity in the presence of external electric fields. The direct measurements of the electric field effect on the fluorescence decay profile suggest that the field-induced deceleration of the nonradiative process contributes to the increase in the fluorescence intensity in the presence of electric fields.

  5. 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

    2015-07-10

    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.

  6. 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.

  7. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

    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.

  9. 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.

  10. 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.

  11. Research of fluorescent spectra of oleic acid-stabilized ZnSe nanocrystals based on UV light modification

    NASA Astrophysics Data System (ADS)

    Hao, Licai; Bai, Zhongchen; Huang, Zhaoliang; Liao, Sha; Zhang, Zhengping

    2016-11-01

    The non-aqueous synthesized and post-preparative treatment of oleic acid (OA)-stabilized ZnSe nanocrystals were studied systematically. ZnSe nanocrystals were successfully synthesized via paraffin liquid and oleic acid system by using OA as stabilizer. Synthesized nanocrystals were characterized by means of absorption and fluorescent spectra, Fourier transform infrared spectrometer, transmission electron microscopy and selected area electron diffraction. Furthermore, solutions of ZnSe nanocrystals were illuminated with UV light. The experimental results showed that the fluorescent peak was red-shifted from 445 to 510 nm. The results suggested that, when the solution under illumination, OA was removed from the surface of ZnSe nanocrystals and the surface of ZnSe nanocrystals was oxidized to ZnO nanocrystals. ZnSe/ZnO core/shell nanocrystals were formed when the solution of ZnSe nanocrystals illuminated with UV light.

  12. 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.

  13. Research on the Terahertz Absorption Spectra of Histidine Enantiomer (L) and its Racemic Compound (DL).

    PubMed

    Zhou, Tao; Wu, Yidong; Cao, Juncheng; Zou, Liangliang; Yuan, Jie; Yao, Zhenwei; Xu, Gongjie

    2017-02-01

    Terahertz time-domain spectroscopy (THz-TDS) is used to investigate the absorption spectra of polycrystalline L- and DL-histidine in the frequency range of 10-100 cm(-1). The spectra exhibit distinct differences in peak frequencies between the enantiomer (L-histidine) and racemic compound (DL-histidine). The observed spectral differences are attributed to the intermolecular interactions. With the density function theory (DFT) method, the frequencies of vibrational modes of L-histidine and DL-histidine in the THz range are calculated and well assigned according to the measured spectra. The origin of the observed vibrational modes is found to be non-localized and of a collective (phonon-like) nature, which points to the lattice and skeleton vibrations mediated by the hydrogen bond. Furthermore, we propose and demonstrate a method for determining the composition ratio of histidine mixtures based on the THz absorption spectra.

  14. 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.

  15. 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.

  16. 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

  17. Estimating the biodegradability of treated sewage samples using synchronous fluorescence spectra.

    PubMed

    Lai, Tien M; Shin, Jae-Ki; Hur, Jin

    2011-01-01

    Synchronous fluorescence spectra (SFS) and the first derivative spectra of the influent versus the effluent wastewater samples were compared and the use of fluorescence indices is suggested as a means to estimate the biodegradability of the effluent wastewater. Three distinct peaks were identified from the SFS of the effluent wastewater samples. Protein-like fluorescence (PLF) was reduced, whereas fulvic and/or humic-like fluorescence (HLF) were enhanced, suggesting that the two fluorescence characteristics may represent biodegradable and refractory components, respectively. Five fluorescence indices were selected for the biodegradability estimation based on the spectral features changing from the influent to the effluent. Among the selected indices, the relative distribution of PLF to the total fluorescence area of SFS (Index II) exhibited the highest correlation coefficient with total organic carbon (TOC)-based biodegradability, which was even higher than those obtained with the traditional oxygen demand-based parameters. A multiple regression analysis using Index II and the area ratio of PLF to HLF (Index III) demonstrated the enhancement of the correlations from 0.558 to 0.711 for TOC-based biodegradability. The multiple regression equation finally obtained was 0.148 × Index II - 4.964 × Index III - 0.001 and 0.046 × Index II - 1.128 × Index III + 0.026. The fluorescence indices proposed here are expected to be utilized for successful development of real-time monitoring using a simple fluorescence sensing device for the biodegradability of treated sewage.

  18. 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

  19. Study of the absorption spectra of Fricke Xylenol Orange gel dosimeters

    SciTech Connect

    Gambarini, Grazia; Artuso, Emanuele; Liosi, Giulia Maria; Giacobbo, Francesca; Mariani, Mari; Brambilla, Luigi; Castiglioni, Chiara; Carrara, Mauro; Pignoli, Emanuele

    2015-07-01

    A systematic study of the absorption spectra of Fricke Xylenol Orange gel dosimeters has been performed, in the wavelength range from 300 nm to 700 nm. The spectrum of Xylenol Orange (without ferrous sulphate solution) has been achieved, in order to subtract its contribution from the absorption spectra of the irradiated Fricke Xylenol Orange gel dosimeters. The absorbance due to ferric ions chelated by Xylenol Orange has been studied for various irradiation doses. Two absorbance peaks are visible, mainly at low doses: the first peak increases with the dose more slowly than the second one. This effect can explain the apparent threshold dose that was frequently evidenced. (authors)

  20. Absorption Spectra of Broadened Sodium Resonance Lines in Presence of Rare Gases

    SciTech Connect

    Chung, H-K; Shurgalin, M; Babb, J F

    2002-09-11

    The pressure broadening of alkali-metal lines is a fundamental problem with numerous applications. For example, the sodium resonance lines broadened by xenon are important in the production of broad spectra emitted in the HPS (High-Pressure Sodium) lamp and they potentially can be used for gas condition diagnostics. Broadened absorption lines of alkali-metal atoms are prominent in the optical spectra of brown dwarfs and understanding the broadening mechanism will help elucidate the chemical composition and atmospheric properties of those stars. The far-line wing spectra of sodium resonance lines broadened by rare gases are found to exhibit molecular characteristics such as satellites and hence the total absorption coefficients for vapors of Na atoms and perturbing rare gas atoms can be modeled as Na-RG (rare gas) molecular absorption spectra. In this work, using carefully chosen interatomic potentials for Na-RG molecules we carry out quantum-mechanical calculations for reduced absorption coefficients for vapors composed of Na-He, Na-Ar, and Na-Xe. Calculated spectra are compared to available experimental results and the agreement is good in the measured satellite positions and shapes.

  1. A novel acoustic sensor approach to classify seeds based on sound absorption spectra.

    PubMed

    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.

  2. 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.

  3. Three-dimensional fluorescence spectra of mineral oil and extraction method of characteristic parameters

    NASA Astrophysics Data System (ADS)

    Shang, Liping; Liu, Xianyong; Xu, Xiaoxuan; Xu, Jingjun

    2005-02-01

    To realize the on-line fluorescence monitoring of mineral oil pollution in water, three-dimensional spectral characteristic of oil-water intermixtures must be studied and the characteristic must be extracted. Using excitation wavelength, fluorescence wavelength and fluorescence intensity as three-dimensional system of coordinate, through sampling and surface fitting, three-dimensional fluorogram is gotten, which can provide gist for oil discrimination when presented in contour chart (finger-print map of oils). But there is little difference between characteristics of three-dimensional fluorogram because of the similarity of constituent and structure of similar oils. Therefore this paper introduces quantitative analysis method-characteristic parameter method which starts with analyzing statistical characteristic of three-dimensional fluorogram. Using RFPC fluorescence spectrometer (Shimadzu, Japan), three-dimensional fluorescence spectra of diesel oil, machine oil, gasoline oil, crude oil are measured and parameterized. The result shows that as a quantitative classified discrimination method of three-dimensional fluorescence spectra, the parameter of characteristic parameter method possesses definiteness for three-dimensional fluorescence spectra, and it is applicable, available when used in oil discrimination.

  4. Evaluation of potential emission spectra for the reliable classification of fluorescently coded materials

    NASA Astrophysics Data System (ADS)

    Brunner, Siegfried; Kargel, Christian

    2011-06-01

    The conservation and efficient use of natural and especially strategic resources like oil and water have become global issues, which increasingly initiate environmental and political activities for comprehensive recycling programs. To effectively reutilize oil-based materials necessary in many industrial fields (e.g. chemical and pharmaceutical industry, automotive, packaging), appropriate methods for a fast and highly reliable automated material identification are required. One non-contacting, color- and shape-independent new technique that eliminates the shortcomings of existing methods is to label materials like plastics with certain combinations of fluorescent markers ("optical codes", "optical fingerprints") incorporated during manufacture. Since time-resolved measurements are complex (and expensive), fluorescent markers must be designed that possess unique spectral signatures. The number of identifiable materials increases with the number of fluorescent markers that can be reliably distinguished within the limited wavelength band available. In this article we shall investigate the reliable detection and classification of fluorescent markers with specific fluorescence emission spectra. These simulated spectra are modeled based on realistic fluorescence spectra acquired from material samples using a modern VNIR spectral imaging system. In order to maximize the number of materials that can be reliably identified, we evaluate the performance of 8 classification algorithms based on different spectral similarity measures. The results help guide the design of appropriate fluorescent markers, optical sensors and the overall measurement system.

  5. [Study on the effect of solar spectra on the retrieval of atmospheric CO2 concentration using high resolution absorption spectra].

    PubMed

    Hu, Zhen-Hua; Huang, Teng; Wang, Ying-Ping; Ding, Lei; Zheng, Hai-Yang; Fang, Li

    2011-06-01

    Taking solar source as radiation in the near-infrared high-resolution absorption spectrum is widely used in remote sensing of atmospheric parameters. The present paper will take retrieval of the concentration of CO2 for example, and study the effect of solar spectra resolution. Retrieving concentrations of CO2 by using high resolution absorption spectra, a method which uses the program provided by AER to calculate the solar spectra at the top of atmosphere as radiation and combine with the HRATS (high resolution atmospheric transmission simulation) to simulate retrieving concentration of CO2. Numerical simulation shows that the accuracy of solar spectrum is important to retrieval, especially in the hyper-resolution spectral retrieavl, and the error of retrieval concentration has poor linear relation with the resolution of observation, but there is a tendency that the decrease in the resolution requires low resolution of solar spectrum. In order to retrieve the concentration of CO2 of atmosphere, the authors' should take full advantage of high-resolution solar spectrum at the top of atmosphere.

  6. 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.

  7. Substituent Effects on the Absorption and Fluorescence Properties of Anthracene.

    PubMed

    Abou-Hatab, Salsabil; Spata, Vincent A; Matsika, Spiridoula

    2017-02-16

    Substitution can be used to efficiently tune the photophysical properties of chromophores. In this study, we examine the effect of substituents on the absorption and fluorescence properties of anthracene. The effects of mono-, di-, and tetrasubstitution of electron-donating and -withdrawing functional groups were explored. In addition, the influence of a donor-acceptor substituent pair and the position of substitution were investigated. Eleven functional groups were varied on positions 1, 2, and 9 of anthracene, and on position 6 of 2-methoxyanthracene and 2-carboxyanthracene. Moreover, the donor-acceptor pair NH2/CO2H was added on different positions of anthracene for additional studies of doubly substituted anthracenes. Finally, we looked into quadruple substitutions on positions 1,4,5,8 and 2,3,6,7. Vertical excitation energies and oscillator strengths were computed using density functional theory with the hybrid CAM-B3LYP functional and 6-311G(d) basis set. Correlations between the excitation energies or oscillator strengths of the low-lying bright La state and the Hammett sigma parameter, σp(+), of the substituents were examined. The energy is red-shifted for all cases of substitution. Oscillator strengths increase when substituents are placed along the direction of the transition dipole moment of the bright La excited state. Substitution of long chain conjugated groups significantly increases the oscillator strength in comparison to the cases for other substituents. In addition, the results of quadruply substituted geometries reveal symmetric substitution at the 1,4,5,8 positions significantly increases the oscillator strength and can lower the band gap compared to that of the unsubstituted anthracene molecule by up to 0.5 eV.

  8. 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.

  9. [High-order derivative spectroscopy of infrared absorption spectra of the reaction centers from Rhodobacter sphaeroides].

    PubMed

    2005-01-01

    The infrared absorption spectra of reduced and chemically oxidized reaction center preparations from the purple bacterium Rhodobacter sphaeroides were investigated by means of high-order derivative spectroscopy. The model Gaussian band with a maximum at 810 nm and a half-band of 15 nm found in the absorption spectrum of the reduced reaction center preparation is eliminated after the oxidation of photoactive bacteriochlorophyll dimer (P). This band was related to the absorption of the P(+)y excitonic band of P. On the basis of experimental results, it was concluded that the bleaching of the P(+)y absorption band at 810 nm in the oxidized reaction center preparations gives the main contribution to the blue shift of the 800 nm absorption band of Rb. sphaeroides reaction centers.

  10. Multivariate discriminating algorithm for analyzing laser-induced fluorescence spectra of human gastrointestinal cancer

    NASA Astrophysics Data System (ADS)

    Chen, Wei; Wei, Guang Hui

    1998-09-01

    The purpose of this study has been to evaluate the laser- induced fluorescence characters of normal and malignant stomach tissue in Vitro and in Vivo. The stepwise multivariate discrimination analysis was used to make a multivariate statistical algorithm for analyzing the diagnostic parameters of human stomach tissues fluorescence spectrum. The resulting spectra could be differentiating histologically stomach abnormal tissue from normal tissue with a sensitivity and specificity value of 95% and 97%. The diagnosis results were in excellent agreement with histopathological results.

  11. 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.

  12. A model considering light reabsorption processes to correct in vivo chlorophyll fluorescence spectra in apples.

    PubMed

    Ramos, María E; Lagorio, María G

    2006-05-01

    Chlorophyll-a contained in the peel of Granny Smith apples emits fluorescence upon excitation with blue light. The observed emission, collected by an external detector and corrected by its spectral response, is still distorted by light reabsorption processes taking place in the fruit skin and differs appreciably from the true spectral distribution of fluorescence emerging from chlorophyll molecules in the biological tissue. Reabsorption processes particularly affect the ratio of fluorescence intensities at 680 nm and at 730 nm. A model to obtain the correct spectral distribution of the emission, from the experimental fluorescence recorded at a fluorometer detector and corrected for the detector spectral sensitivity, is developed in the present work. Measurements of the whole fruit reflectance, the peel transmittance and the flesh reflectance allow the calculation of the reabsorption-corrected spectra. The model is validated by comparing the corrected emission spectra with that obtained for a thin layer of apple-peel-chloroplasts, where no reabsorption takes place. It is recommended to correct distortions in emission spectra of intact fruits due to light reabsorption effects whenever a correlation between the physiological state of the fruit and its fluorescence spectra is investigated.

  13. Synthesis and infrared and fluorescent spectra of rare earth complexes with a new amide ligand.

    PubMed

    Cui, Haixia; Chen, Jianmin; Zhou, Huidi; Lu, Yanhua

    2007-11-01

    Solid complexes of rare earth nitrates and picrates with a new amide ligand, 1,6-bis[(2'-benzylaminoformyl)phenoxyl]hexane (L) have been prepared. These complexes are characterized by elemental analysis, UV-vis spectra and IR spectra. The fluorescent and luminescent properties of the Eu(III) and Tb(III) nitrates and picrates complexes in solid state are also investigated. Under the excitation of UV light, these complexes except Tb(III) picrate complex exhibit characteristic emission of europium and terbium ions. The influence of the counter anion on the fluorescent intensity is also discussed.

  14. 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.

  15. Excited states and absorption spectra of β-diketonate complexes of boron difluoride with aromatic substituents

    NASA Astrophysics Data System (ADS)

    Vovna, V. I.; Kazachek, M. V.; L'vov, I. B.

    2012-04-01

    In the approximation of the time-dependent electron density functional theory, we have studied using the quantum-chemical method the nature of excited states of boron difluoride acetylacetonate F2BAA and its substituted derivatives that contain aromatic groups with one or two benzene cycles in the β-position. Optimization of the geometry of complexes show coplanar positions of cycles for all compounds, except for that with the substituent C6H3(CH3)2. Based on the calculated transition energies and oscillator strengths, we have simulated the absorption spectra in the prevacuum range. The calculated absorption spectra have been compared with the experimental spectra in the gas phase or in solutions. We show that, in the absorption spectra of complexes that contain substituents with one benzene cycle, the first three bands are caused by the transition of π electrons of the substituent to the LUMO of the chelate cycle. In complexes with two cycles in the substituent, the number of these transitions increases to five. As the π system becomes more extended, a bathochromic shift of the first absorption band and an increase in the transition probability are observed.

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

    NASA Astrophysics Data System (ADS)

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

    2012-07-01

    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 μm 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.

  17. Understanding the features in the ultrafast transient absorption spectra of CdSe quantum dots

    NASA Astrophysics Data System (ADS)

    Zhang, Cheng; Do, Thanh Nhut; Ong, Xuanwei; Chan, Yinthai; Tan, Howe-Siang

    2016-12-01

    We describe a model to explain the features of the ultrafast transient absorption (TA) spectra of CdSe core type quantum dots (QDs). The measured TA spectrum consists of contributions by the ground state bleach (GSB), stimulated emission (SE) and excited state absorption (ESA) processes associated with the three lowest energy transition of the QDs. We model the shapes of the GSB, SE and ESA spectral components after fits to the linear absorption. The spectral positions of the ESA components take into account the biexcitonic binding energy. In order to obtain the correct weightage of the GSB, SE and ESA components to the TA spectrum, we enumerate the set of coherence transfer pathways associated with these processes. From our fits of the experimental TA spectra of 65 Å diameter QDs, biexcitonic binding energies for the three lowest energy transitions are obtained.

  18. Solvent and structural effects on the UV absorption spectra of N-(substituted phenyl)-2-cyanoacetamides.

    PubMed

    Matijević, Borko M; Vaštag, Đenđi Đ; Perišić-Janjić, Nada U; Apostolov, Suzana Lj; Milčić, Miloš K; Živanović, Lidija; Marinković, Aleksandar D

    2014-01-03

    UV absorption spectra of N-(substituted phenyl)-2-cyanoacetamides have been recorded in the range 200-400 nm in the set of selected solvents. The solute-solvent interactions were analyzed on the basis of linear solvation energy relationships (LSER) concept proposed by Kamlet and Taft. The effects of substituents on the absorption spectra were interpreted by correlation of absorption frequencies with Hammett substituent constant, σ. It was found that substituents significantly change the extent of conjugation. Furthermore, the experimental findings were interpreted with the aid of ab initio B3LYP/6-311G(d,p) method. Electronic energies was calculated by the use of 6-311++G(3df,3pd) methods with standard polarized continuum model (PCM) for inclusion of the solvent effect.

  19. 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.

  20. 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.

  1. Delta bilirubin: absorption spectra, molar absorptivity, and reactivity in the diazo reaction.

    PubMed

    Doumas, B T; Wu, T W; Jendrzejczak, B

    1987-06-01

    Delta bilirubin (B delta), isolated from serum, has an absorption maximum near 440 nm and a molar absorptivity of 72,000 L mol-1cm-1 in either Tris HCl (0.1 mol/L, pH 8.5) or phosphate (0.13 mol/L, pH 7.4) buffer. This absorptivity exceeds by approximately 50% and 59%, respectively, that of unconjugated bilirubin in the same buffers. This finding suggests that substantial errors can be incurred in direct spectrophotometry of bilirubins in serum. In the total diazo (TBIL) assay (Clin Chem 1985;31:1779-89), the color yield from B delta increases by 10% as the final diazo concentration is increased from 0.27 to 0.81 mmol/L. In the direct (DBIL) assay, if done in HCl (50 mmol/L), B delta yields approximately 15% more color as the diazo concentration is increased from 0.51 to 1.53 mmol/L, whereas in acetate buffer (0.4 mol/L, pH 4.7) the corresponding color yield is 25% greater. However, the absolute color yield for the reaction in HCl exceeds that in acetate buffer. In both the TBIL and the DBIL assay, B delta reacts slowly, nearly complete reaction requiring 10 min. Thus, B delta may be seriously underestimated in diazo (especially DBIL) methods in which short reaction times (20 s to 1 min) are used.

  2. Modeling biological fluorescence emission spectra using Lorentz line shapes and nonlinear optimization

    NASA Astrophysics Data System (ADS)

    Nation, Paul D.; Howard, A. Q.; Webb, Lincoln J.

    2007-08-01

    Using the Levenberg-Marquardt nonlinear optimization algorithm and a series of Lorentzian line shapes, the fluorescence emission spectra from BG (Bacillus globigii) bacteria can be accurately modeled. This method allows data from both laboratory and field sources to model the return signal from biological aerosols using a typical LIF (lidar induced fluorescence) system. The variables found through this procedure match individual fluorescence components within the biological material and therefore have a physically meaningful interpretation. The use of this method also removes the need to calculate phase angles needed in autoregressive all-pole models.

  3. Dye-doped sol-gel materials for two-photon absorption induced fluorescence

    NASA Astrophysics Data System (ADS)

    Canva, Michael; Roger, Gisèle; Cassagne, Florence; Lévy, Yves; Brun, Alain; Chaput, Frédéric; Boilot, Jean-Pierre; Rapaport, Alexandra; Heerdt, Céline; Bass, Michael

    2002-01-01

    Two-photon absorption (TPA) and subsequent fluorescence properties of laser dyes are retained when doped into solid state sol-gel materials. These properties were demonstrated to be applicable in true 3D displays.

  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. 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.

  6. 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.

  7. Computer Simulation of the far Infrared Collision Induced Absorption Spectra of Gaseous CO2

    NASA Technical Reports Server (NTRS)

    Gruszka, Marcin; Borysow, Aleksandra

    1998-01-01

    Far infrared collision induced absorption spectra of gaseous CO2 were computed using molecular dynamics simulations. The quadrupole and hexadecapole multipolar induction, through the trace, and the anisotropy of the molecular polarizability were found to be insufficient to represent properly the dipole induction mechanism. For a detailed analysis of the induction process the spectra obtained were decomposed into components resulting from different terms of the induced dipole. Based on this decomposition, all additional overlap contribution for each term was proposed. When spectra were recomputed including such overlap, good agreement between experiment and simulation was achieved over the temperature range at which measurements exist (233-400 K). The use of an anisotropic intermolecular potential was found to be of critical importance for obtaining the right shape of the far wings of the spectra.

  8. Infrared absorption and Raman scattering spectra of water under pressure via first principles molecular dynamics.

    PubMed

    Ikeda, Takashi

    2014-07-28

    From both the polarized and depolarized Raman scattering spectra of supercritical water a peak located at around 1600 cm(-1), attributed normally to bending mode of water molecules, was experimentally observed to vanish, whereas the corresponding peak remains clearly visible in the measured infrared (IR) absorption spectrum. In this computational study a theoretical formulation for analyzing the IR and Raman spectra is developed via first principles molecular dynamics combined with the modern polarization theory. We demonstrate that the experimentally observed peculiar behavior of the IR and Raman spectra for water are well reproduced in our computational scheme. We discuss the origins of a feature observed at 1600 cm(-1) in Raman spectra of ambient water.

  9. SimBAL: A Spectral Synthesis Approach to Analyzing Broad Absorption Line Quasar Spectra

    NASA Astrophysics Data System (ADS)

    Terndrup, Donald M.; Leighly, Karen; Gallagher, Sarah; Richards, Gordon T.

    2017-01-01

    Broad Absorption Line quasars (BALQSOs) show blueshifted absorption lines in their rest-UV spectra, indicating powerful winds emerging from the central engine. These winds are essential part of quasars: they can carry away angular momentum and thus facilitate accretion through a disk, they can distribute chemically-enriched gas through the intergalactic medium, and they may inject kinetic energy to the host galaxy, influencing its evolution. The traditional method of analyzing BALQSO spectra involves measuring myriad absorption lines, computing the inferred ionic column densities in each feature, and comparing with the output of photonionization models. This method is inefficient and does not handle line blending well. We introduce SimBAL, a spectral synthesis fitting method for BALQSOs, which compares synthetic spectra created from photoionization model results with continuum-normalized observed spectra using Bayesian model calibration. We find that we can obtain an excellent fit to the UV to near-IR spectrum of the low-redshift BALQSO SDSS J0850+4451, including lines from diverse ionization states such as PV, CIII*, SIII, Lyalpha, NV, SiIV, CIV, MgII, and HeI*.

  10. 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.

  11. 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.

  12. 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.

  13. 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

  14. Absorption and fluorescence characteristics of photo-activated adenylate cyclase nano-clusters from the amoeboflagellate Naegleria gruberi NEG-M strain

    NASA Astrophysics Data System (ADS)

    Penzkofer, A.; Stierl, M.; Hegemann, P.; Kateriya, S.

    2012-01-01

    The spectroscopic characteristics of BLUF (BLUF = sensor of blue light using flavin) domain containing soluble adenylate cyclase (nPAC = Naegleria photo-activated cyclase) samples from the amoeboflagellate Naegleria gruberi NEG-M strain is studied at room temperature. The absorption and fluorescence spectroscopic development in the dark was investigated over two weeks. Attenuation coefficient spectra, fluorescence quantum distributions, fluorescence quantum yields, and fluorescence excitation distributions were measured. Thawing of frozen nPAC samples gave solutions with varying protein nano-cluster size and varying flavin, tyrosine, tryptophan, and protein color-center emission. Protein color-center emission was observed in the wavelength range of 360-900 nm with narrow emission bands of small Stokes shift and broad emission bands of large Stokes shift. The emission spectra evolved in time with protein nano-cluster aging.

  15. Vibrational dynamics of DNA. II. Deuterium exchange effects and simulated IR absorption spectra

    NASA Astrophysics Data System (ADS)

    Lee, Chewook; Cho, Minhaeng

    2006-09-01

    In Paper I, we studied vibrational properties of normal bases, base derivatives, Watson-Crick base pairs, and multiple layer base pair stacks in the frequency range of 1400-1800cm-1. However, typical IR absorption spectra of single- and double-stranded DNA have been measured in D2O solution. Consequently, the more relevant bases and base pairs are those with deuterium atoms in replacement with labile amino hydrogen atoms. Thus, we have carried out density functional theory vibrational analyses of properly deuterated bases, base pairs, and stacked base pair systems. In the frequency range of interest, both aromatic ring deformation modes and carbonyl stretching modes appear to be strongly IR active. Basis mode frequencies and vibrational coupling constants are newly determined and used to numerically simulate IR absorption spectra. It turns out that the hydration effects on vibrational spectra are important. The numerically simulated vibrational spectra are directly compared with experiments. Also, the O18-isotope exchange effect on the poly(dG):poly(dC) spectrum is quantitatively described. The present calculation results will be used to further simulate two-dimensional IR photon echo spectra of DNA oligomers in the companion Paper III.

  16. 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.

  17. Remote sensing of trace constituents from atmospheric infrared emission and absorption spectra

    NASA Technical Reports Server (NTRS)

    Barker, D. B.; Brooks, J. N.; Goldman, A.; Kosters, J. J.; Murcray, D. G.; Murcray, F. H.; Van Allen, J.; Williams, W. J.

    1976-01-01

    Atmospheric infrared emission and absorption spectra obtained from aircraft and balloon-borne spectrometers are presented. From such spectra, mixing ratio vs altitude profiles are derived for several minor constituents. Recent results for HNO3, CF2Cl2, CFCl3, and HF are presented. In addition, the feasibility of infrared detection of other trace constituents, such as HCl, HF, NH3, NO and SO2, against the rest of the atmospheric background is studied. From this study, made on a line-by-line basis for 'state of the art' airborne spectrometers, potential spectral features for detection of the trace constituents are isolated.

  18. Optical Absorption Spectra of Ternary Complex of Praseodymium in Different Environment

    NASA Astrophysics Data System (ADS)

    Gupta, Anup Kumar; Ujjwal, Shri Kishan

    The optical absorption spectra of complex of Praseodymium in different solvents i.e water, Methanol, Ethanol & Acetic Acid have been recorded in visible region (360-620 nm for Pr3+) using amino acid as primary ligand and diol as secondary ligand. The value of energies & intensities of various transitions have been calculated using Judd-Ofelt relation is in good agreement with experimental result. The study of complex found it to be covalent in nature. The spectra in visible region have been recorded on model uv-2601 Rayleigh analytical instrument corp.

  19. Identification of acetylene (C2H2) in infrared atmospheric absorption spectra

    NASA Astrophysics Data System (ADS)

    Goldman, A.; Murcray, F. J.; Blatherwick, R. D.; Gillis, J. R.; Bonomo, F. S.; Murcray, F. H.; Murcray, D. G.; Cicerone, R. J.

    1981-12-01

    Infrared atmospheric absorption spectra at ˜0.02 cm-1 resolution obtained during a balloon flight made on March 23, 1981, show absorption features attributable to C2H2. These features are used to derive a preliminary mixing ratio of ˜25 pptv near 9 km. This mixing ratio falls into the range of values we calculate for upper tropospheric C2H2 in a photochemical/transport model but well below values measured previously in samples collected by other researchers.

  20. Identification of acetylene /C2H2/ in infrared atmospheric absorption spectra

    NASA Technical Reports Server (NTRS)

    Goldman, A.; Murcray, F. J.; Blatherwick, R. D.; Gillis, J. R.; Bonomo, F. S.; Murcray, F. H.; Murcray, D. G.; Cicerone, R. J.

    1981-01-01

    Infrared atmospheric absorption spectra at 0.02/cm resolution were obtained during a balloon flight on March 23, 1981 from the Holloman AFB, New Mexico. The absorption features, attributed to C2H2, were used to derive a preliminary mixing ratio of about 25 pptv near 9 km, accurate to + or - 40%. This mixing ratio falls into the range of values calculated for the upper troposphere C2H2 in a photochemical/transport model. However, previous measurements from aircraft grab sampling (Cronn and Robinson, 1979) show four to twelve times this C2H2 concentration 1.5 km below the tropopause.

  1. In vivo low-coherence spectroscopic measurements of local hemoglobin absorption spectra in human skin

    NASA Astrophysics Data System (ADS)

    Bosschaart, Nienke; Faber, Dirk J.; van Leeuwen, Ton G.; Aalders, Maurice C. G.

    2011-10-01

    Localized spectroscopic measurements of optical properties are invaluable for diagnostic applications that involve layered tissue structures, but conventional spectroscopic techniques lack exact control over the size and depth of the probed tissue volume. We show that low-coherence spectroscopy (LCS) overcomes these limitations by measuring local attenuation and absorption coefficient spectra in layered phantoms. In addition, we demonstrate the first in vivo LCS measurements of the human epidermis and dermis only. From the measured absorption in two distinct regions of the dermal microcirculation, we determine total hemoglobin concentration (3.0+/-0.5 g/l and 7.8+/-1.2 g/l) and oxygen saturation.

  2. Intervening Mg II absorption systems from the SDSS DR12 quasar spectra

    NASA Astrophysics Data System (ADS)

    Raghunathan, Srinivasan; Clowes, Roger G.; Campusano, Luis E.; Söchting, Ilona K.; Graham, Matthew J.; Williger, Gerard M.

    2016-12-01

    We present the catalogue of the Mg II absorption systems detected at a high significance level using an automated search algorithm in the spectra of quasars from the 12th data release of the Sloan Digital Sky Survey. A total of 266,433 background quasars were searched for the presence of absorption systems in their spectra. The continuum modelling for the quasar spectra was performed using a mean filter. A pseudo-continuum derived using a median filter was used to trace the emission lines. The absorption system catalogue contains 39,694 Mg II systems detected at a 6.0, 3.0σ level respectively for the two lines of the doublet. The catalogue was constrained to an absorption line redshift of 0.35 ≤ z2796 ≤ 2.3. The rest-frame equivalent width of the λ2796 line ranges between 0.2 ≤ Wr ≤ 6.2 Å. Using Gaussian noise-only simulations, we estimate a false positive rate of 7.7 per cent in the catalogue. We measured the number density ∂N2796/∂z of Mg II absorbers and find evidence for steeper evolution of the systems with Wr ≥ 1.2 Å at low redshifts (z2796 ≤ 1.0), consistent with other earlier studies. A suite of null tests over the redshift range 0.5 ≤ z2796 ≤ 1.5 was used to study the presence of systematics and selection effects like the dependence of the number density evolution of the absorption systems on the properties of the background quasar spectra. The null tests do not indicate the presence of any selection effects in the absorption catalogue if the quasars with spectral signal-to-noise level less than 5.0 are removed. The resultant catalogue contains 36,981 absorption systems. The Mg II absorption catalogue is publicly available and can be downloaded from the link http://srini.ph.unimelb.edu.au/mgii.php.

  3. In vivo low-coherence spectroscopic measurements of local hemoglobin absorption spectra in human skin.

    PubMed

    Bosschaart, Nienke; Faber, Dirk J; van Leeuwen, Ton G; Aalders, Maurice C G

    2011-10-01

    Localized spectroscopic measurements of optical properties are invaluable for diagnostic applications that involve layered tissue structures, but conventional spectroscopic techniques lack exact control over the size and depth of the probed tissue volume. We show that low-coherence spectroscopy (LCS) overcomes these limitations by measuring local attenuation and absorption coefficient spectra in layered phantoms. In addition, we demonstrate the first in vivo LCS measurements of the human epidermis and dermis only. From the measured absorption in two distinct regions of the dermal microcirculation, we determine total hemoglobin concentration (3.0±0.5 g∕l and 7.8±1.2 g∕l) and oxygen saturation.

  4. Measurements of trace constituents from atmospheric infrared emission and absorption spectra, a feasibility study

    NASA Technical Reports Server (NTRS)

    Goldman, A.; Williams, W. J.; Murcray, D. G.

    1974-01-01

    The feasibility of detecting eight trace constituents (CH4, HCl, HF, HNO3, NH3, NO, NO2 and SO2) against the rest of the atmospheric background at various altitudes from infrared emission and absorption atmospheric spectra was studied. Line-by-line calculations and observational data were used to establish features that can be observed in the atmospheric spectrum due to each trace constituent. Model calculations were made for experimental conditions which approximately represent state of the art emission and absorption spectrometers.

  5. Scalar and vector collisional interference in the vibration-rotation absorption spectra of H2 and HD

    NASA Technical Reports Server (NTRS)

    Herman, R. M.

    1987-01-01

    The only atomic or molecular spectra known to exhibit 'collisional interference' effects are those of H2 and its isotopes. Attention is presently given to the sharp absorption spectra of HD, which demonstrate collisional interference effects is a fashion that while surprising has been experimentally verified and theoretically characterized in detail. Collisional interference can dramatically alter the line shapes usually encountered in dipole absorption spectra, while nevertheless remaining narrow.

  6. 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.

  7. Far-ultraviolet absorption spectra of quasars: How to find missing hot gas and metals

    NASA Technical Reports Server (NTRS)

    Verner, D. A.; Tytler, David; Barthel, P. D.

    1994-01-01

    We show that some high-redshift QSO absorption systems that reveal only the H I Lyman series lines at wavelengths visible from the ground maybe a new class of ultra-high-ionization metal line systems, with metal lines in the far-UV region which is now being explored with satellites. At high temperatures or in intense radiation fields metal systems will not show the usual C IV absorption, and O VI will become the most prominent metal absorber. At still higher ionization, O IV also becomes weak and the strongest metal lines are from Ne VIII, Mg X and Si XII, which have doublets in the rangs 500-800 A. Hence very high ionization metal systems will not show metal lines in existing spectra. Recent X-ray observations show that galaxy halos contain hot gas, so we predict that far-UV spectra of QSOs will also show this gas.

  8. Three-dimensional time-dependent wave-packet calculations of OBrO absorption spectra

    NASA Astrophysics Data System (ADS)

    Yuan, Kai-Jun; Sun, Zhigang; Cong, Shu-Lin; Lou, Nanquan

    2005-08-01

    The absorption spectra of the C(A22)←X(B12) transition of the OBrO molecule are calculated using three-dimensional time-dependent wave-packet method in Radau coordinates for a total angular momentum J =0. The wave packet is propagated using the split operator technique associated with fast Fourier transform. Employing the basis functions obtained by one-dimensional Fourier grid Hamiltonian method, the initial wave packet is calculated directly on the three-dimensional Fourier grid. The numerical model is characterized by simplicity and efficiency. The ab initio potential surfaces for the C(A22) and X(B12) states are used in the calculation. The calculated absorption spectra of the C(A22)←X(B12) transition of OBrO molecule agree well with the experimental results.

  9. 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.

  10. Absorption Spectra of Fe, Mn, and Mg Water Complexes Calculated Using Density Functional Theory

    DTIC Science & Technology

    2013-08-20

    the calculated absorption spectra of isolated molecules can help to identify intramolecular vibrational modes of various materials. A series of...Transformation A molecule in 3-dimensions has a total of 3N-6 normal mode vibrations . The Schrodinger equation for the harmonic...oscillations of these normal modes has known solutions. The quantum mechanical spectrum of each of these vibrations is given in the harmonic approximation

  11. Ab initio study of optical absorption spectra of semiconductors and conjugated polymers

    SciTech Connect

    Tiago, M.L.; Chang, Eric K.; Rohlfing, Michael; Louie, Steven G.

    2000-04-30

    The effects of electron-hole interaction on the optical properties of a variety of materials have been calculated using an ab initio method based on solving the Bethe-Salpeter equation. Results on selected semiconductors, insulators, and semiconducting polymers are presented. In the cases of alpha-quartz (SiO2) and poly-phenylene-vinylene, resonant excitonic states qualitatively alter the absorption spectra.

  12. 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

  13. Absorption and Luminescence Studies of Some Highly Fluorescent Derivatives of Vitamin B1; Solvent and pH Effects

    NASA Astrophysics Data System (ADS)

    Marciniak, B.; Koput, J.; Kozubek, H.

    1990-08-01

    The influence of solvent on the UV-visible absorption and luminescence spectra of some highly fluorescent vitamin B1 derivatives, the products of the reaction of N-methylated vitamin B1 with cytidine (I), adenosine (II) and 2-amino-4-methylpyridine (III) is studied. Spectroscopic manifestations of protonation of I and II are also investigated using a semiempirical INDO/S CI method. Singlet and triplet energy levels of the free ion and several protonated species are calculated, and transition energies and oscillator strengths are compared with the experimental spectra. Calculated charge densities on heteroatoms in the ground and excited singlet and triplet states are correlated with changes of the experimental pKa values with excitation. The results for I and II are compared with those for the trimethylated pyrichrominium ion (III) previously studied

  14. Algae (Microcystis and Scenedesmus) absorption spectra and its application on Chlorophyll a retrieval

    NASA Astrophysics Data System (ADS)

    Wu, Di; Chen, Maosi; Wang, Qiao; Gao, Wei

    2013-12-01

    Blue algae and green algae are the dominant phytoplankton groups that contribute to the eutrophication and the water bloom in inland water of China. The absorption coefficients (spectra) of the algae, which do not change with its intrinsic optical characteristics and the observation geometry, are strictly additive quantities. The characteristics of the absorption spectra of the two algae are presented. The pure blue algae and the pure green algae cultured in the laboratory environment are diluted and mixed at ten volume ratios. The Quantitative Filter Technique was applied to measure their absorption spectra. The "hot-ethanol extraction" method was chosen to calculate their concentration of Chlorophyll a. The retrieval algorithm developed in this study extracts the mapping information between each individual alga and their Chlorophyll a concentration via Continuous Wavelet Transform, and retrieves the Chlorophyll a concentration of each alga in their mixture using a trust region optimizer. The results show that the retrieved and the measured Chlorophyll a concentrations of the blue algae and the green algae components in the ten mixture match well with the average relative error of 5.55%.

  15. 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.

  16. Modeling of multi-exciton transient absorption spectra of protochlorophyllide aggregates in aqueous solution.

    PubMed

    Sytina, Olga A; Novoderezhkin, Vladimir I; van Grondelle, Rienk; Groot, Marie Louise

    2011-11-03

    Protochlorophyllide (Pchlide) is a natural porphyrin, a precursor of chlorophyll, synthesized by plants for its photosynthetic apparatus. The pigment spontaneously forms aggregates when dissolved in neat water solution. We present here calculations of the transient absorption spectra and its comprising components (ground-state bleach, stimulated emission, and excited-state absorption) for a strongly excitonically coupled linear chain of four Pchlide chromophores, using exciton theory with phenomenological Gaussian line shapes and without energetic disorder. A refined multiexciton model that includes static disorder is applied to fit the experimental power-dependent transient absorption spectra of aqueous protochlorophyllide and the kinetics for delay times up to 20 ps after photoexcitation. We show that population up to the 4-exciton manifold is sufficient to explain the pronounced saturation of the bleaching and the shape changes in the instantaneous, t = 0.2 ps transient spectra when the pulse energy is increased from 10 to 430 nJ per pulse. The decay of the multiexciton manifold is relatively slow and is preceded by a spectroscopically distinct process. We suggest that the exciton states in the Pchlide aggregates are mixed with charge-transfer states (CTS) and that the population and repopulation of the CTS coupled to the exciton states explains the relatively slow decay of the multiexciton manifold. The relevance of our results to the optical properties and dynamics of natural photosynthetic complexes and the possible physical origin of CTS formation are discussed.

  17. The electronic absorption spectra of pyridine azides, solvent-solute interaction.

    PubMed

    Abu-Eittah, Rafie H; Khedr, Mahmoud K

    2009-01-01

    The electronic absorption spectra of: 2-, 3-, and 4-azidopyridines have been investigated in a wide variety of polar and non-polar solvents. According to Onsager model, the studied spectra indicate that the orientation polarization of solvent dipoles affects the electronic spectrum much stronger than the induction polarization of solvent dipoles. The effect of solvent dipole moment predominates that of solvent refractive index in determining the values of band maxima of an electronic spectrum. The spectra of azidopyridines differ basically from these of pyridine or mono-substituted pyridine. Results at hand indicate that the azide group perturbs the pyridine ring in the case of 3-azidopyridine much more than it does in the case of 2-azidopyridine. This result agrees with the predictions of the resonance theory. Although the equilibrium <==> azide tetrazole is well known, yet the observed spectra prove that such an equilibrium does not exist at the studied conditions. The spectra of the studied azidopyridines are characterized by the existence of overlapping transitions. Gaussian analysis is used to obtain nice, resolved spectra. All the observed bands correspond to pi-->pi* transitions, n-->pi* may be overlapped with the stronger pi-->pi* ones.

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. Quantitative photoacoustic microscopy of optical absorption coefficients from acoustic spectra in the optical diffusive regime.

    PubMed

    Guo, Zijian; Favazza, Christopher; Garcia-Uribe, Alejandro; Wang, Lihong V

    2012-06-01

    Photoacoustic (PA) microscopy (PAM) can image optical absorption contrast with ultrasonic spatial resolution in the optical diffusive regime. Conventionally, accurate quantification in PAM requires knowledge of the optical fluence attenuation, acoustic pressure attenuation, and detection bandwidth. We circumvent this requirement by quantifying the optical absorption coefficients from the acoustic spectra of PA signals acquired at multiple optical wavelengths. With the acoustic spectral method, the absorption coefficients of an oxygenated bovine blood phantom at 560, 565, 570, and 575 nm were quantified with errors of <3%. We also quantified the total hemoglobin concentration and hemoglobin oxygen saturation in a live mouse. Compared with the conventional amplitude method, the acoustic spectral method provides greater quantification accuracy in the optical diffusive regime. The limitations of the acoustic spectral method was also discussed.

  4. Investigation of relations between skin cancer lesions' images and their fluorescent spectra

    NASA Astrophysics Data System (ADS)

    Pavlova, P.; Borisova, E.; Avramov, L.; Petkova, El.; Troyanova, P.

    2010-03-01

    This investigation is based on images obtained from healthy tissue and skin cancer lesions and their fluorescent spectra of cutaneous lesions derived after optical stimulation. Our analyses show that the lesions’ spectra of are different of those, obtained from normal tissue and the differences depend on the type of cancer. We use a comparison between these “healthy” and “unhealthy” spectra to define forms of variations and corresponding diseases. However, the value of the emitted light varies not only between the patients, but also depending on the position of the tested area inside of one lesion. These variations could be result from two reasons: different degree of damaging and different thickness of the suspicious lesion area. Regarded to the visible image of the lesion, it could be connected with the chroma of colour of the tested area and the lesion homogeneity that corresponds to particular disease. For our investigation, images and spectra of three non-melanoma cutanous malignant tumors are investigated, namely—basal cell carcinoma, squamous cell carcinoma, and keratoacanthoma. The images were processed obtaining the chroma by elimination of the background—healthy tissue, and applying it as a basic signal for transformation from RGB to Lab colorimetric model. The chroma of the areas of emission is compared with the relative value of fluorescence spectra. Specific spectral features are used to develop hybrid diagnostic algorithm (including image and spectral features) for differentiation of these three kinds of malignant cutaneous pathologies.

  5. Implications of New Methane Absorption Coefficients on Uranus Vertical Structure Derived from Near-IR Spectra

    NASA Astrophysics Data System (ADS)

    Fry, Patrick M.; Sromovsky, L. A.

    2009-09-01

    Using new methane absorption coefficients from Karkoschka and Tomasko (2009, submitted to Icarus, "Methane Absorption Coefficients for the Jovian Planets from Laboratory, Huygens, and HST Data"), we fit Uranus near-IR spectra previously analyzed in Sromovsky et al. (2006, Icarus 182, 577-593, Fink and Larson, 1979 J- and H-band), Sromovsky and Fry (2008, Icarus 193, 252-266, 2006 NIRC2 J- and H-band, 2006 SpeX) using Irwin et al. (2006, Icarus 181, 309-319) methane absorption coefficients. Because the new absorption coefficients usually result in higher opacities at the low temperatures seen in Uranus' upper troposphere, our previously derived cloud altitudes are expected to generally rise to higher altitudes. For example, using Lindal et al. (1987, JGR 92, 14987-15001) model D temperature and methane abundance profiles, we are better able to fit the J-band 43-deg. south bright band with the new coefficients (chi-square=205, vs. 315 for Irwin), with the pressure of the upper tropospheric cloud decreasing to 1.6 bars (from 2.4 bars using Irwin coefficients). Improvements in fitting H-band spectra from the same latitude are not as readily obtained. Derived upper tropospheric cloud pressures are very similar using the two absorption datasets (1.6-1.7 bars), but the character of the fits differs. New Karkoschka and Tomasko coefficients better fit some details in the 1.5-1.58 micron region, but Irwin fits the broad absorption band wing at 1.61-1.62 microns better, and the fit chi-square values are similar (K&T: 243, Irwin: 220). Results for a higher methane concentration (Lindal et al. model F) were similar. Whether the new coefficients will simply raise derived altitudes across the planet or will result in fundamental changes in structure is as yet unclear. This work was suported by NASA planetary astronomy and planetary atmospheres programs.

  6. 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.

  7. Effects of ozone and relative humidity on fluorescence spectra of octapeptide bioaerosol particles

    NASA Astrophysics Data System (ADS)

    Pan, Yong-Le; Santarpia, Joshua L.; Ratnesar-Shumate, Shanna; Corson, Elizabeth; Eshbaugh, Jonathan; Hill, Steven C.; Williamson, Chatt C.; Coleman, Mark; Bare, Christopher; Kinahan, Sean

    2014-01-01

    The effects of ozone and relative humidity (RH) at common atmospheric levels on the properties of single octapeptide bioaerosol particles were studied using an improved rotating reaction chamber, an aerosol generator, an ultraviolet aerodynamic particle sizer (UVAPS), an improved single particle fluorescence spectrometer (SPFS), and equipments to generate, monitor and control the ozone and RH. Aerosol particles (mean diameter 2 μm) were generated from a slurry of octapeptide in phosphate buffered saline, injected into the rotating chamber, and kept airborne for hours. Bioaerosols were sampled from the chamber hourly for the measurements of particle-size distribution, concentration, total fluorescence excited at 355-nm, and single particle fluorescence spectra excited at 266-nm and 351-nm under different controlled RH (20%, 50%, or 80%) and ozone concentration (0 or 150 ppb). The results show that: (1) Particle size, concentration, and the 263-nm-excited fluorescence intensity decrease at different rates under different combinations of the RH and ozone concentrations used. (2) The 263-nm-excited UV fluorescence (280-400 nm) decreased more rapidly than the 263-nm-excited visible fluorescence (400-560 nm), and decreased most rapidly when ozone is present and RH is high. (3) The UV fluorescence peak near 340 nm slightly shifts to the shorter wavelength (blue-shift), consistent with a more rapid oxidation of tryptophan than tyrosine. (4) The 351/355-nm-excited fluorescence (430-580 nm/380-700 nm) increases when ozone is present, especially when the RH is high. (5) The 351/355-nm-excited fluorescence increase that occurs as the tryptophan emission in the UV decreases, and the observation that these changes occur more rapidly at higher RH with the present of ozone, are consistent with the oxidation of tryptophan by ozone and the conversion of the resulting ozonides to N-formyl kynurenine and kynurenine.

  8. 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.

  9. Study of preferential solvation of 2,6-diaminoanthraquinone in binary mixtures by absorption and fluorescence studies

    NASA Astrophysics Data System (ADS)

    Sasirekha, V.; Ramakrishnan, V.

    2008-08-01

    The role of solute-solvent and solvent-solvent interaction on the preferential solvation characteristics of 2,6-diaminoanthraquinone (DAAQ) has been analysed by monitoring the optical absorption and fluorescence emission spectra. Binary mixtures consist of dimethylformamide (DMF)-ethanol (EtOH), DMF-dimelthylsulfoxide (DMSO), benzene (BZ)-DMF and acetonitrile (ACN)-DMF. The optical absorption spectra maximum and emission spectra maximum of DAAQ show the changes with varying the solvents and change in the composition in the case of binary mixtures. Non-ideal solvation characteristics are observed in all binary mixtures. It is found that at certain concentrations two mixed solvents interact to form a common structure with a ν12 (wave number in cm -1) value not always intermediate ( ν1 and ν2) between the values of the solvents mixed. Synergistic effect is observed in the case of DMF-EtOH mixtures. The preferential solvation parameters local mole fraction X2L, solvation index δS2, exchange constant K12 are calculated in all binary mixtures expect in the case of DMF-BZ mixture and DMF-EtOH mixture in the ground state. We have also monitored excitation wavelength effect on the probe molecule in aprotic polar and protic polar solvents.

  10. Composite Spectra of Broad Absorption Line Quasars in SDSS-III BOSS

    NASA Astrophysics Data System (ADS)

    Herbst, Hanna; Hamann, Fred; Paris, Isabelle; Capellupo, Daniel M.

    2017-01-01

    We present preliminary results from a study of broad absorption line (BAL) quasars in the SDSS-III BOSS survey. We’re particularly interested in BALs because they arise from quasar outflows, which may be a source of feedback to the host galaxy. We analyze median composite spectra for BOSS QSOs in the redshift range 2.1 to 3.4 sorted by the strength of the BAL absorption troughs, parameterized by the Balnicity Index (BI), to study trends in the emission and absorption properties of BAL quasars. The wavelength coverage and high number of quasars observed in the BOSS survey allow us to examine BALs in the Lyman forest. Our main preliminary results when sorting the quasars by BI are 1) doublet absorption lines such as P V 1128A show a 1:1 ratio across all BI, indicating large column densities at all BI. This suggests that weaker BAL troughs result from smaller covering fractions rather than lower column densities. 2) The He II emission line, which is a measure of the far-UV/near-UV hardness of the ionizing continuum, is weaker in the larger BI composite spectra, indicating a far-UV spectral softening correlated with BI. This is consistent with the radiatively-driven BAL outflows being helped by intrinsically weaker ionizing continuum shapes (e.g., Baskin, Laor, and Hamann 2013). We also find a trend for slightly redder continuum slopes in the larger BI composite spectra, suggesting that the slope differences in the near-UV are also intrinsic.

  11. 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.

  12. The minimizing of fluorescence background in Raman optical activity and Raman spectra of human blood plasma.

    PubMed

    Tatarkovič, Michal; Synytsya, Alla; Šťovíčková, Lucie; Bunganič, Bohuš; Miškovičová, Michaela; Petruželka, Luboš; Setnička, Vladimír

    2015-02-01

    Raman optical activity (ROA) is inherently sensitive to the secondary structure of biomolecules, which makes it a method of interest for finding new approaches to clinical applications based on blood plasma analysis, for instance the diagnostics of several protein-misfolding diseases. Unfortunately, real blood plasma exhibits strong background fluorescence when excited at 532 nm; hence, measuring the ROA spectra appears to be impossible. Therefore, we established a suitable method using a combination of kinetic quenchers, filtering, photobleaching, and a mathematical correction of residual fluorescence. Our method reduced the background fluorescence approximately by 90%, which allowed speedup for each measurement by an average of 50%. In addition, the signal-to-noise ratio was significantly increased, while the baseline distortion remained low. We assume that our method is suitable for the investigation of human blood plasma by ROA and may lead to the development of a new tool for clinical diagnostics.

  13. 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.

  14. 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

  15. 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

  16. Assessing the maturity of crude petroleum oils using total synchronous fluorescence scan spectra.

    PubMed

    Ryder, Alan G

    2004-01-01

    There have been many applications of fluorescence methods for the analysis of crude petroleum oils down through the years. However, none of these studies has yielded a robust qualitative or quantitative method for quantifying the chemical composition, or assessing the maturity of crude oils. Simple fluorescence parameters such as lifetime, intensity, and intensity ratios do not correlate well with chemical composition particularly for medium weight crude oils [A. G. Ryder, T. J. Glynn, and M. Feely (2003). Proc. SPIE-Int. Soc. Opt. Eng. 4876, 1188-1195.]. A better approach may be to use the Total Synchronous Fluorescence Scan (TSFS) method to fully interrogate the complex chemical composition of the oils [D. Patra and A. K. Mishra (2002). Anal. Bioanal. Chem. 373, 304-309.]. We present TSFS spectra from 18 crude petroleum oils of varying composition, sourced from around the world. The TSFS plots of these oils are very complex, with the contours being spread over the full 250-700 nm wavelength range (lambda(ex)) and 40-200 nm wavelength interval (delta lambda) sampled. The 3-D contour maps tend to two contour concentrations one at lambda(em) < 300 nm, delta lambda = 120-200 nm, and a second near lambda(ex) approximately 380-400 nm, delta lambda = 40-60 nm. The first feature represents fluorescence emission originating mainly from energy transfer processes with the second, longer wavelength feature originating from fluorescence emission generated by a higher proportion of direct excitation as opposed to emission resulting from energy transfer. The topography of the 3D contour plots is therefore influenced by the balance between energy transfer and direct fluorescence emission, which is governed by the chemical composition of the crude oils. We discuss how the gross chemical composition affects TSFS spectra and how TSFS can be used to assess oil maturity with a view to developing quantitative methods.

  17. 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.

  18. 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.

  19. Infrared absorption spectra, radiative efficiencies, and global warming potentials of perfluorocarbons: Comparison between experiment and theory

    NASA Astrophysics Data System (ADS)

    Bravo, IváN.; Aranda, Alfonso; Hurley, Michael D.; Marston, George; Nutt, David R.; Shine, Keith P.; Smith, Kevin; Wallington, Timothy J.

    2010-12-01

    Experimentally and theoretically determined infrared spectra are reported for a series of straight-chain perfluorocarbons: C2F6, C3F8, C4F10, C5F12, C6F14, and C8F18. Theoretical spectra were determined using both density functional (DFT) and ab initio methods. Radiative efficiencies (REs) were determined using the method of Pinnock et al. (1995) and combined with atmospheric lifetimes from the literature to determine global warming potentials (GWPs). Theoretically determined absorption cross sections were within 10% of experimentally determined values. Despite being much less computationally expensive, DFT calculations were generally found to perform better than ab initio methods. There is a strong wavenumber dependence of radiative forcing in the region of the fundamental C-F vibration, and small differences in wavelength between band positions determined by theory and experiment have a significant impact on the REs. We apply an empirical correction to the theoretical spectra and then test this correction on a number of branched chain and cyclic perfluoroalkanes. We then compute absorption cross sections, REs, and GWPs for an additional set of perfluoroalkenes.

  20. 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.

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

    PubMed

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

    2014-09-08

    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.

  2. Comparison between IR absorption and raman scattering spectra of liquid and supercritical 1-butanol.

    PubMed

    Sokolova, Maia; Barlow, Stephen J; Bondarenko, Galina V; Gorbaty, Yuri E; Poliakoff, Martyn

    2006-03-23

    Raman spectra of 1-butanol have been obtained at a constant pressure of 500 bar up to 350 degrees C and along isotherms 250, 300, and 350 degrees C up to 600 bar. The purpose of the experiment was to compare responses of Raman and IR absorption spectroscopy to the forming of O-H...O bonds in alcohols. As a result, some important inferences were drawn from the experiment. In particular, it has been estimated quantitatively how the intensity of Raman scattering in the region of the OH band depends on the extent of hydrogen bonding. As might be expected, the dependence is much weaker than in the case of the IR absorption. As was shown, the ratio of integrated intensities of bonded molecules in the absorption and scattering spectra is a constant and does not depend on temperature and density. The effect of cooperativity of hydrogen bonds is confirmed. It was also found that even at high pressures, a noticeable amount of nonbonded molecules exists at room temperature.

  3. Possible use of pattern recognition for the analysis of Mars rover X-ray fluorescence spectra

    NASA Technical Reports Server (NTRS)

    Yin, Lo I; Trombka, Jacob I.; Seltzer, Stephen M.; Johnson, Robert G.; Philpotts, John A.

    1989-01-01

    On the Mars rover sample-return mission, the rover vehicle will collect and select samples from different locations on the Martian surface to be brought back to earth for laboratory studies. It is anticipated that an in situ energy-dispersive X-ray fluorescence (XRF) spectrometer will be on board the rover. On such a mission, sample selection is of higher priority than in situ quantitative chemical anlaysis. With this in mind, a pattern recognition technique is proposed as a simple, direct, and speedy alternative to detailed chemical analysis of the XRF spectra. The validity and efficacy of the pattern recognition technique are demonstrated by the analyses of laboratory XRF spectra obtained from a series of geological samples, in the form both of standardized pressed pellets and as unprepared rocks. It is found that pattern recognition techniques applied to the raw XRF spectra can provide for the same discrimination among samples as a knowledge of their actual chemical composition.

  4. Possible use of pattern recognition for the analysis of Mars rover X ray fluorescence spectra

    NASA Astrophysics Data System (ADS)

    Trombka, Jacob I.; Seltzer, Stephen M.; Johnson, Robert G.; Philpotts, John A.

    1989-10-01

    On the Mars rover sample return mission the rover vehicle will collect and select samples from different locations on the Martial surface to be brought back to Earth for laboratory studies. It is anticipated that an in situ energy-dispersive X ray fluorescence (XRF) spectrometer will be on board the rover. On such a mission, sample selection is of higher priority than in situ quantitative chemical analysis. With this in mind we propose pattern recognition as a simple, direct, and speedy alternative to detailed chemical analysis of the XRF spectra. The validity and efficacy of the pattern recognition technique are demonstrated by the analyses of laboratory XRF spectra obtained from a series of geological samples, in the form both of standardized pressed pellets and as unprepared rocks. It is found that pattern recognition techniques applied to the raw XRF spectra can provide for the same discrimination among samples as knowledge of their actual chemical composition.

  5. 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.

  6. 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.

  7. Simulations of X-ray absorption spectra: the effect of the solvent.

    PubMed

    Penfold, Thomas J; Curchod, Basile F E; Tavernelli, Ivano; Abela, Rafael; Rothlisberger, Ursula; Chergui, Majed

    2012-07-14

    We perform quantum mechanics/molecular mechanics molecular dynamics simulations on the [Pt(2)(P(2)O(5)H(2))(4)](4-) (abbreviated PtPOP) complex; in water, dimethylformamide and ethanol. These are used to calculate the ground state X-ray absorption spectrum of the complex. The structural parameters from X-ray spectra are usually extracted using a fit of the experimental data. In such simulations the solvent is neglected meaning that any effect of the local environment will be compensated for by structural changes of the solute, leading to possible discrepancies in the extracted structural parameters. Our simulations show a significant solvent effect on the spectra, which has important implications for the structural analysis of molecules in solution.

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

    PubMed

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

    2013-05-15

    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.

  9. Multiple-scattering approach to the x-ray-absorption spectra of 3d transition metals

    NASA Astrophysics Data System (ADS)

    Kitamura, Michihide; Muramatsu, Shinji; Sugiura, Chikara

    1986-04-01

    The x-ray-absorption near-edge structure (XANES) has been calculated for the 3d transition metals Cr, Fe, Ni, and Cu from a multiple-scattering approach within the muffin-tin-potential approximation, as a first step to studying the XANES for complicated materials. The muffin-tin potential is constructed via the Mattheiss prescription using the atomic data of Herman and Skillman. It is found that the XANES is sensitive to the potential used and that the calculated XANES spectra reproduce the number of peaks and their separations observed experimentally. The final spectra, including the lifetime-broadening effect, show the general features of each material. We emphasize that the multiple-scattering theory which can be applied to the disordered systems as well as the ordered ones may be promising as a tool to analyze the XANES of complicated materials.

  10. Quantitation of DNA and RNA with Absorption and Fluorescence Spectroscopy.

    PubMed

    Gallagher, Sean R

    2017-02-02

    Quantitation of nucleic acids is a fundamental tool in molecular biology that requires accuracy, reliability, and the use of increasingly smaller sample volumes. This unit describes the traditional absorbance measurement at 260 nm and three more sensitive fluorescence techniques employing Hoechst 33258, ethidium bromide, and PicoGreen. The range of the assays covers 25 pg/ml to 50 µg/ml. Absorbance at 260 nm has an effective range from 1 to 50 µg/ml; Hoechst 33258 from 0.01 to 15 µg/ml; ethidium bromide from 0.1 to 10 µg/ml; and PicoGreen from 25 to 1000 pg/ml. © 2017 by John Wiley & Sons, Inc.

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

    PubMed

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

    2010-03-01

    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 microm(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.

  12. 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.

  13. Paradoxical solvent effects on the absorption and emission spectra of amino-substituted perylene monoimides.

    PubMed

    Zoon, Peter D; Brouwer, Albert M

    2005-08-12

    In N-(2,5-di-tert-butylphenyl)-9-pyrrolidinoperylene-3,4-dicarboximide (5PI) the absorption and emission spectra display large solvatochromic shifts, but, remarkably, the Stokes shift is practically independent of solvent polarity. This unique behavior is caused by the extraordinarily large ground-state dipole moment of 5PI, which further increases upon increasing the solvent polarity, whereas the excited-state dipole moment is less solvent dependent. In the corresponding piperidine compound, 6PI, this effect is much less important owing to the weaker coupling between the amino group and the aromatic imide moiety, and in the corresponding naphthalimide, 5NI, it is absent. The latter shows the conventional solvatochromic behavior of a push-pull substituted conjugated system, that is, minor shifts in absorption and a larger change in the emission energy with solvent polarity.

  14. The X-shooter sample of GRB afterglow spectra: Properties of the absorption features

    NASA Astrophysics Data System (ADS)

    de Ugarte Postigo, Antonio

    2015-08-01

    Since its commissioning at ESO's Very Large Telescope in 2009, the X-shooter spectrograph has become the reference instrument in gamma-ray burst (GRB) afterglow spectroscopy. During this time our collaboration has collected more than 70 spectra of GRB afterglows, with redshifts ranging from 0.06 to 6.3. Thanks to their extreme luminosity and simple intrinsic shape, GRB spectra are optimal tools for the study of galactic environments at basically any redshift. Being produced by the death of short-lived massive stars, they are also tracers of star formation.I will present the sample of absorption spectral features identified in X-shooter's GRB spectra describing observation and analysis techniques. The different features are compared with the characteristics of the explosion (duration, spectral shape, energetics, etc.) and with the properties of the host galaxy (mass, age, etc.) to improve our understanding of the nature of the explosions and how they interact with their environments. Using the large redshift range of the spectra collection we perform studies of the evolution of GRB environments across the history of the Universe and their relation with the evolution of star formation.

  15. 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.

  16. Gain and Absorption Spectra of Quantum Wire Lasers Diodes Grown on Nonplanar Substrates

    DTIC Science & Technology

    1992-04-01

    SIMMJ^ COMPONENT PART NOTICE THIS PAPER IS A COMPONENT PART OF THE FOLLOWING COMPILATION REPORT: TTT1F: Integrated Photonics Research. Volume 10...i’t’y Co" .,.*» Dist kl Avji. :.;;fl,’or Spital ulll’MAR85Mb:> OPI: DTIC-TID Integrated Photonics Research -1 Gain and Absorption Spectra of...modulators and switches. 92-31749 Integrated Photonics Research 59 MC2-2 References: 1. E. Kapon, D.M. Hwang and R. Bhat, Phys. Rev. Lett. 63, 430 (1989

  17. Quantum-chemical investigation of the structure and electronic absorption spectra of electroluminescent zinc complexes

    NASA Astrophysics Data System (ADS)

    Minaev, B. F.; Baryshnikov, G. V.; Korop, A. A.; Minaeva, V. A.; Kaplunov, M. G.

    2013-01-01

    Using the quantum chemical methods of the density functional theory and of the electron density topological analysis, we have studied the structure of two recently synthesized electroluminescent zinc complexes, one with aminoquinoline ligands and the other with a Schiff base (N,O-donor). The energies and intensities of vertical excitations for the molecules under study have been calculated in terms of the PM3 semiempirical approximation taking into account the configurational interaction between singly excited singlet excited states. Good agreement between calculation results and experimental data on the electron density topological characteristics and on the visible and UV absorption spectra has been obtained.

  18. Solvent effects on the electronic absorption spectra and acid strength of some substituted pyridinols

    NASA Astrophysics Data System (ADS)

    Hashem, Elham Y.; Saleh, Magda S.

    2002-01-01

    The electronic absorption spectra of some substituted pyridinols in organic solvents of different polarities are studied. Also, the solvent effects on the intramolecular charge transfer bands are discussed using various solvent parameters. The acid-base equilibria of the compounds used are studied spectrophotometrically in various mixed aqueous solvents at 25 °C and 0.1 M ionic strength (NaClO 4). Furthermore, the influence of the solvents on the dissociation constants and tautomeric equilibria of a pyridinol derivatives are discussed. The effect of molecular structure of the pyridinols on the p K's is also examined.

  19. 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.

  20. A Survey for Intervening CIV Absorption-Line Systems Using SDSS Quasar Spectra

    NASA Astrophysics Data System (ADS)

    Monier, Eric M.; Nestor, D. B.; Daino, M. M.; Quider, A. M.; Rao, S. M.; Turnshek, D. A.

    2006-06-01

    Intervening CIV absorption-line systems are readily found in Sloan Digital Sky Survey (SDSS) quasar spectra at redshifts z > 1.5. Given the large number of absorbers, high statistical accuracy is possible in comparison to what was possible in the past. Here we present preliminary results on the incidence and evolution of the CIV systems as a function of CIV rest equivalent width. The absorber incidence is proportional to the product of gas cross-section and co-moving number density of absorbers, while the rest equivalent width is related to their kinematic spread. We discuss the interpretation of our results.

  1. Disentangling atomic-layer-specific x-ray absorption spectra by Auger electron diffraction spectroscopy

    NASA Astrophysics Data System (ADS)

    Matsui, Fumihiko; Matsushita, Tomohiro; Kato, Yukako; Hashimoto, Mie; Daimon, Hiroshi

    2009-11-01

    In order to investigate the electronic and magnetic structures of each atomic layer at subsurface, we have proposed a new method, Auger electron diffraction spectroscopy, which is the combination of x-ray absorption spectroscopy (XAS) and Auger electron diffraction (AED) techniques. We have measured a series of Ni LMM AED patterns of the Ni film grown on Cu(001) surface for various thicknesses. Then we deduced a set of atomic-layer-specific AED patterns in a numerical way. Furthermore, we developed an algorithm to disentangle XANES spectra from different atomic layers using these atomic-layer-specific AED patterns. Surface and subsurface core level shift were determined for each atomic layer.

  2. The energy calibration of x-ray absorption spectra using multiple-beam diffraction

    SciTech Connect

    Hagelstein, M.; Cunis, S. ); Frahm, R. ); Rabe, P. )

    1992-01-01

    A new method for calibrating the energy scale of x-ray absorption spectra from an energy dispersive spectrometer has been developed. Distinct features in the diffracted intensity of the curved silicon crystal monochromator have been assigned to multiple-beam diffraction. The photon energies of these structures can be calculated if the precise spacing of the diffracting planes and the orientation of the crystal relative to the incident synchrotron radiation are known. The evaluation of Miller indices of operative reflections and the calculation of the corresponding photon energy is presented. The assignment of operative reflexes is simplified if the monochromator crystal can be rotated around the main diffracting vector {bold H}.

  3. Resonant Photoemission and M_{2,3}-Absorption Spectra in Nickel Dichloride

    NASA Astrophysics Data System (ADS)

    Igarashi, J.

    Ni 3p-resonant photoemission and Ni M_{2,3}-absorption spectra are calculated in detail on a cluster of (NiCl_6)^{4-} with the use of the transition matrix elements evaluated on the Herman-Skillman potential in Ni atom. Overall spectral shape agrees well with experiment, allowing a determination of the parameters which characterize Ni 3d and Cl 3p states. Resonance behavior is discussed near the Ni 3p-core level photothreshold. The resonant enhancement is found to be larger for the peak with higher binding energy in the d^7-multiplets.

  4. Absorption and resonance Raman spectra of Pb2, Pb3 and Pb4 in xenon matrices

    NASA Technical Reports Server (NTRS)

    Stranz, D. D.; Khanna, R. K.

    1980-01-01

    Lead metal was vaporized and trapped in solid xenon at 12K. Electronic absorption and resonance Raman spectra were recorded of the resulting matrix, which was shown to contain Pb2, Pb3, and possibly Pb4 molecular species. The vibrational frequency for Pb2 is determined to be 108/cm for the ground state, with a dissociation energy of 82000/cm. Ad3h symmetry is indicated for the Pb3 species, with nu sub 1=117/cm and nu sub 2 = 96 /cm. The existence of Pb4 is suggested by a fundamental and overtone of 111/cm spacing.

  5. A ubiquitous absorption feature in the X-ray spectra of BL Lacertae objects

    NASA Technical Reports Server (NTRS)

    Madejski, Greg M.; Mushotzky, Richard F.; Weaver, Kimberly A.; Arnaud, Keith A.; Urry, C. Megan

    1991-01-01

    The paper presents the broadband (0.5-20-keV) X-ray spectra of five X-ray bright BL Lac objects observed with the Einstein Observatory Solid State Spectrometer (SSS) and Monitor Proportional Counter (MPC) detectors. The combination of moderate energy resolution and broad spectral coverage makes it possible to confirm the presence of an absorption feature at an energy of 650 eV in the BL Lac object PKS 2155-304, originally reported by Canizares and Kruper (1984) based on higher resolution Einstein Objective Grating Spectrometer (OGS) data.

  6. Modulated microwave absorption spectra from Josephson junctions on a scratched niobium wire

    SciTech Connect

    Rubins, R.S. |; Hutton, S.L.; Ravindran, K.; Subbaraman, K.; Drumheller, J.E.

    1997-05-01

    Modulated microwave absorption (MMA) spectra from Josephson junction formations on a scratched Nb wire have been studied at 9.3 GHz and 4 K. The peak-to-peak separation, {delta}H of the Josephson lines was found to vary linearly with P{sup 1/2}, where P is the applied microwave power, in contrast to a recent interpretation of junction formation in pressed lead pieces by Rubins, Drumheller, and Trybula. The interpretation of the MMA data on Nb are given in terms of the theory of Vichery, Beuneu, and Lejay for superconducting loops containing weak links. {copyright} {ital 1997} {ital The American Physical Society}

  7. The Intervening Galaxies Hypothesis of the Absorption Spectra of Quasi-Stellar Objects: Some Statistical Studies

    NASA Astrophysics Data System (ADS)

    Duari, Debiprosad; Narlikar, Jayant V.

    This paper examines, in the light of the available data, the hypothesis that the heavy element absorption line systems in the spectra of QSOs originate through en-route absorption by intervening galaxies, halos etc. Several statistical tests are applied in two different ways to compare the predictions of the intervening galaxies hypothesis (IGH) with actual observations. The database is taken from a recent 1991 compilation of absorption line systems by Junkkarinen, Hewitt and Burbidge. Although, prima facie, a considerable gap is found between the predictions of the intervening galaxies hypothesis and the actual observations despite inclusion of any effects of clustering and some likely selection effects, the gap narrows after invoking evolution in the number density of absorbers and allowing for the incompleteness and inhomogeneity of samples examined. On the latter count the gap might be bridgeable by stretching the parameters of the theory. It is concluded that although the intervening galaxies hypothesis is a possible natural explanation to account for the absorption line systems and may in fact do so in several cases, it seems too simplistic to be able to account for all the available data. It is further stressed that the statistical techniques described here will be useful for future studies of complete and homogenous samples with a view to deciding the extent of applicability of the IGH.

  8. 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.

  9. Ultrabright fluorescent silica particles with a large number of complex spectra excited with a single wavelength for multiplex applications.

    PubMed

    Palantavida, S; Peng, B; Sokolov, I

    2017-02-08

    We report on a novel approach to synthesize ultrabright fluorescent silica particles capable of producing a large number of complex spectra. The spectra can be excited using a single wavelength which is paramount in quantitative fluorescence imaging, flow cytometry and sensing applications. The approach employs the physical encapsulation of organic fluorescent molecules inside a nanoporous silica matrix with no dye leakage. As was recently demonstrated, such an encapsulation allowed for the encapsulation of very high concentrations of organic dyes without quenching their fluorescent efficiency. As a result, dye molecules are distanced within ∼5 nm from each other; it theoretically allows for efficient exchange of excitation energy via Förster resonance energy transfer (FRET). Here we present the first experimental demonstration of the encapsulation of fluorescent dyes in the FRET sequence. Attaining a FRET sequence of up to five different dyes is presented. The number of distinguishable spectra can be further increased by using different relative concentrations of encapsulated dyes. Combining these approaches allows for creating a large number of ultrabright fluorescent particles with substantially different fluorescence spectra. We also demonstrate the utilization of these particles for potential multiplexing applications. Though fluorescence spectra of the obtained multiplex probes are typically overlapping, they can be distinguished by using standard linear decomposition algorithms.

  10. 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

  11. Self-absorption Effects on Alpha-Induced Atmospheric Nitrogen Fluorescence Yield

    SciTech Connect

    Bachelor, Paula P.; Jordan, David V.; Harper, Warren W.; Cannon, Bret D.; Finn, Erin C.

    2009-12-01

    Nitrogen fluorescence induced by alpha, beta and gamma radiation can be used to detect the presence of radioactive contamination in the environment. Successful measurement of fluorescence yield involves a number of factors, including: known fluorescence signal rate during the measurement; the effective alpha spectrum of the radioactive sources used in the measurement; optical attenuation length of the fluorescence signal in air during the measurement; the absolute throughput of the instrumentation; calibration of the instrumentation; and radiation transport modeling of the "effective" array exposure rate given the spectrum of the alpha particles. Field testing of optical instrumentation was conducted to measure the nitrogen fluorescence yield from the alpha radiation generated from americium-241 (241Am) decay. The 241Am test sources were prepared by direct evaporation of ~1 mCi in nitric acid solution, and some solids were visible on the surface of the sources. A laboratory study was conducted with lower activities of 241Am to determine whether the presence of solids on the surface of the sources prepared both by direct evaporation and by electrodeposition onto stainless steel disks produced sufficient self-absorption to cause a decrease in expected fluorescence. Alpha spectroscopy was used to determine the apparent activity of the sources versus the known activity deposited on the surface. Results from the self-absorption laboratory studies were used to correct the activity values in the model and calculate the nitrogen fluorescence generated by the 241Am during the field experiments.

  12. 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.

  13. 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.

  14. Variability in chlorophyll fluorescence spectra of eggplant fruit grown under different light environments: a case study.

    PubMed

    Ospina Calvo, Brian; Parapugna, Tamara L; Lagorio, M Gabriela

    2017-03-13

    The main goal of the present work was to clarify physiological strategies in plants whose chloroplasts were developed under different light environments. The specific objective was to elucidate the influence of the spectral distribution of light on the chlorophyll fluorescence ratio and on photosynthetic parameters. To achieve this purpose, three species of eggplant fruit (black, purple and white striped and white) were used as a case study and their chlorophyll fluorescence was analyzed in detail. Spectra of the non-variable fluorescence in each part of the fruit were corrected for distortions by light reabsorption processes using a physical model. The main conclusion of this work was that the corrected fluorescence ratio was dependent on the contribution of each photosystem to the fluorescence and consequently on the environmental lighting conditions, becoming higher when illumination was rich in long wavelengths. Variable chlorophyll fluorescence, similar to that observed from plant leaves, was detected for the pulp of the black eggplant, for the pulp of the purple and white striped eggplant and for the intact fruit of the black eggplant. The maximum quantum efficiency of photosystem II in the light-adapted state (F'v/F'm), the quantum efficiency of photosystem II (ΦPSII), and the photochemical and non-photochemical quenching coefficients (qP and qNP/NPQ respectively) were determined in each case. The results could be explained very interestingly, in relation with the proportion of exciting light reaching each photosystem (I and II). The photochemical parameters obtained from variable chlorophyll fluorescence, allowed us to monitor non-destructively the physiological state of the black fruit during storage under both chilled or room-temperature conditions.

  15. 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.

  16. Absorption Spectrum of the Green Fluorescent Protein Chromophore Anion In Vacuo

    NASA Astrophysics Data System (ADS)

    Nielsen, S. B.; Lapierre, A.; Andersen, J. U.; Pedersen, U. V.; Tomita, S.; Andersen, L. H.

    2001-11-01

    A sensitive photoabsorption technique for studies of gas-phase biomolecules has been used at the ELISA electrostatic heavy-ion storage ring. We show that the anion form of the chromophore of the green fluorescent protein in vacuo has an absorption maximum at 479 nm, which coincides with one of the two absorption peaks of the protein. Its absorption characteristics are therefore ascribed to intrinsic chemical properties of the chromophore. Evidently, the special β-can structure of the protein provides shielding of the chromophore from the surroundings without significantly changing the electronic structure of the chromophore through interactions with amino acid side chains.

  17. 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.

  18. A support vector machine approach to the automatic identification of fluorescence spectra emitted by biological agents

    NASA Astrophysics Data System (ADS)

    Gelfusa, M.; Murari, A.; Lungaroni, M.; Malizia, A.; Parracino, S.; Peluso, E.; Cenciarelli, O.; Carestia, M.; Pizzoferrato, R.; Vega, J.; Gaudio, P.

    2016-10-01

    Two of the major new concerns of modern societies are biosecurity and biosafety. Several biological agents (BAs) such as toxins, bacteria, viruses, fungi and parasites are able to cause damage to living systems either humans, animals or plants. Optical techniques, in particular LIght Detection And Ranging (LIDAR), based on the transmission of laser pulses and analysis of the return signals, can be successfully applied to monitoring the release of biological agents into the atmosphere. It is well known that most of biological agents tend to emit specific fluorescence spectra, which in principle allow their detection and identification, if excited by light of the appropriate wavelength. For these reasons, the detection of the UVLight Induced Fluorescence (UV-LIF) emitted by BAs is particularly promising. On the other hand, the stand-off detection of BAs poses a series of challenging issues; one of the most severe is the automatic discrimination between various agents which emit very similar fluorescence spectra. In this paper, a new data analysis method, based on a combination of advanced filtering techniques and Support Vector Machines, is described. The proposed approach covers all the aspects of the data analysis process, from filtering and denoising to automatic recognition of the agents. A systematic series of numerical tests has been performed to assess the potential and limits of the proposed methodology. The first investigations of experimental data have already given very encouraging results.

  19. 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

  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. 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…

  2. 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

  3. Absorption in X-ray spectra of high-redshift quasars

    NASA Technical Reports Server (NTRS)

    Elvis, Martin; Fiore, Fabrizio; Wilkes, Belinda; Mcdowell, Jonathan; Bechtold, Jill

    1994-01-01

    We present evidence that X-ray absorption is common in high-redshift quasars. We have studied six high-redshift (z approximately 3) quasars with the ROSAT Position Sensitive Proportional Counter (PSPC) of which four are in directions of low Galactic N(sub H). Three out of these four show excess absorption, while only three in approximately 50 z approximately less than 0.4 quasars do, indicating that such absorption must be common, but not ubiquitous, at high redshifts, and that the absorbers must lie at z greater than 0.4. The six quasars were: S5 0014+81, Q0420-388, PKS 0438-436, S4 0636+680. PKS 2000-330, PKS 2126-158, which have redshifts between 2.85 and 3.78. PKS 0438-436 and PKS 2126-158 show evidence for absorption above the local Galactic value at better than 99.999% confidence level. If the absorber is at the redshift of the quasar, then values of N(sub H) = (0.86(+0.49, -0.28)) x 10(exp 22) atoms/sq cm for PKS 0438-436, and N(sub H) = (1.45(+1.20, -0.64)) x 10(exp 22) atoms/ sq cm for PKS 2126-158, are implied, assuming solar abundances. The spectrum of S4 0636+680 also suggests the presence of a similarly large absorption column density at the 98% confidence level. This absorption reverses the trend for the most luminous active galactic nuclei (AGN) to have the least X-ray absorption, so a new mechanism is likely to be responsible. Intervening absorption due to damped Lyman(alpha) systems is a plausible cause. We also suggest, as an intrinsic model, that intracluster material, e.g., a cooling flow, around the quasar could account for both the X-ray spectrum and other properties of these quasars. All the quasars are radio-loud and three are gigahertz peaked (two of the three showing absorption). No excess absorption above the Galactic value is seen toward Q0420-388. This quasar has two damped Lyman(alpha) systems at z = 3.08. The limit on the X-ray column density implies a low ionization fraction, N(H I)/N(H) approximately greater than 4 x 10(exp -3) (3

  4. 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.

  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. K-edge x-ray absorption spectra of Cs and Xe

    SciTech Connect

    Gomilsek, J. Padeznik; Kodre, A.; Arcon, I.; Hribar, M.

    2003-10-01

    X-ray absorption spectrum of cesium vapor in the K-edge region is measured in a stainless steel cell. The spectrum is free of the x-ray absorption fine structure signal and shows small features analogous to those in the spectrum of the neighbor noble gas Xe. Although the large natural width of the K vacancy (>10 eV) washes out most of the details, fingerprints of multielectron excitations can be recognized at energies close to Dirac-Fock estimates of doubly excited states 1s4(d,p,s) and 1s3(d,p). Among these, the 1s3p excitation 1000 eV above the K edge in both spectra is the deepest double excitation observed so far. Within the K-edge profile, some resolution is recovered with numerical deconvolution of the spectra, revealing the coexcitation of the 5(p,s) electrons, and even the valence 6s electron in Cs. As in homologue elements, three-electron excitations, either as separate channels or as configuration admixtures are required to explain some spectral features in detail.

  7. 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.

  8. A wavelet analysis for the X-ray absorption spectra of molecules.

    PubMed

    Penfold, T J; Tavernelli, I; Milne, C J; Reinhard, M; El Nahhas, A; Abela, R; Rothlisberger, U; 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)(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.

  9. 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.

  10. First principles absorption spectra of Cu{sub n} (n = 2 - 20) clusters.

    SciTech Connect

    Baishya, K.; Idrobo, J. C.; Ogut, S.; Yang, M.; Jackson, K. A.; Jellinek, J.

    2011-06-17

    Optical absorption spectra for the computed ground state structures of copper clusters (Cu{sub n}, n = 2-20) are investigated from first principles using time-dependent density functional theory in the adiabatic local density approximation (TDLDA). The results are compared with available experimental data, existing calculations, and with results from our previous computations on silver and gold clusters. The main effects of d electrons on the absorption spectra, quenching the oscillator strengths, and getting directly involved in low-energy excitations increase in going from Ag{sub n} to Au{sub n} to Cu{sub n} due to the increase in the hybridization of the occupied, yet shallow, d orbitals and the partially occupied s orbitals. We predict that while Cu nanoparticles of spherical or moderately ellipsoidal shape do not exhibit Mie (surface plasmon) resonances, unlike the case for Ag and Au, extremely prolate or oblate Cu nanoparticles with eccentricities near unity should give rise to Mie resonances in the lower end of the visible range and in the infrared. This tunable resonance predicted by the classical Mie-Gans theory is reproduced with remarkable accuracy by our TDLDA computations on hypothetical Cu clusters in the form of zigzag chains with as few as 6 to 20 atoms.

  11. 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.

  12. Nucleic acid vibrational circular dichroism, absorption, and linear dichroism spectra. I. A DeVoe theory approach.

    PubMed Central

    Self, B D; Moore, D S

    1997-01-01

    Infrared (IR) vibrational circular dichroism (VCD), absorption, and linear dichroism (LD) spectra of four homopolyribonucleotides, poly(rA), poly(rG), poly(rC), and poly(rU), have been calculated, in the 1750-1550 cm-1 spectral region, using the DeVoe polarizability theory. A newly derived algorithm, which approximates the Hilbert transform of imaginaries to reals, was used in the calculations to obtain real parts of oscillator polarizabilities associated with each normal mode. The calculated spectra of the polynucleotides were compared with previously measured solution spectra. The good agreement between calculated and measured polynucleotide spectra indicates, for the first time, that the DeVoe theory is a useful means of calculating the VCD and IR absorption spectra of polynucleotides. For the first time, calculated DeVoe theory VCD and IR absorption spectra of oriented polynucleotides are presented. The calculated VCD spectra for the oriented polynucleotides are used to predict the spectra for such measurements made in the future. The calculated IR spectra for the oriented polynucleotides are useful in interpreting the linear dichroism of the polynucleotides. PMID:9199798

  13. 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.

  14. Raman scattering and fluorescence spectra of water from the sea surface microlayer

    NASA Astrophysics Data System (ADS)

    Fadeev, V. V.; Burikov, S. A.; Volkov, P. A.; Lapshin, V. B.; Syroeshkin, A. V.

    2009-04-01

    The Raman scattering and fluorescence spectra were first obtained for the water of sea surface microlayers (SML) of 1 and 0.2 mm thickness (sampled with a Garrett net and a Lapshin capillary sampler, respectively). For reference, samples of water below the SML (from the layer of 0.5 m) were also taken. Substantial differences were found for the values of the normalized intensity of the fluorescence (the number of photons from the volume unit in response to a unit of excitation) between the aqueous humic substances and, presumably, oil hydrocarbons and proteins. Some slight but analyzable differences in the shapes and location of spectral bands were also found. These latter allow one to determine the content of salts and the characteristics of complicated organic compounds in the SML and to compare them to those within the water volume.

  15. Continuous Fluorescence Imaging of Intracellular Calcium by Use of Ion-Selective Nanospheres with Adjustable Spectra.

    PubMed

    Yang, Chenye; Qin, Yu; Jiang, Dechen; Chen, Hong-Yuan

    2016-08-10

    Continuous fluorescence imaging of intracellular ions in various spectral ranges is important for biological studies. In this paper, fluorescent calcium-selective nanospheres, including calix[4]arene-functionalized bodipy (CBDP) or 9-(diethylamino)-5-[(2-octyldecyl)imino]benzo[a]phenoxazine (ETH 5350) as the chromoionophore, were prepared to demonstrate intracellular calcium imaging in visible or near-IR regions, respectively. The fluorescence of the nanospheres was controlled by the chromoionophore, and thus the spectral range for detection was adjustable by choosing the proper chromoionophore. The response time of the nanospheres to calcium was typically 1 s, which allowed accurate measurement of intracellular calcium. These nanospheres were loaded into cells through free endocytosis and exhibited fluorescence for 24 h, and their intensity was correlated with the elevation of intracellular calcium upon stimulation. The successful demonstration of calcium imaging by use of ion-selective nanospheres within two spectral ranges in 24 h supported that these nanospheres could be applied for continuous imaging of intracellular ions with adjustable spectra.

  16. Use of Soller slits to remove reference foil fluorescence from transmission spectra.

    PubMed

    Tse, Justin J; George, Graham N; Pickering, Ingrid J

    2011-05-01

    Measurement of X-ray absorption spectroscopy (XAS) in transmission is the method of choice for strong or concentrated samples. In a typical XAS experiment above 5 keV the sample is placed between the first (I(0)) and second (I(1)) ion chambers and a standard foil is placed between the second (I(1)) and third (I(2)) ion chambers for simultaneous calibration of energy during sample analysis. However, some fluorescence from the foil may be registered in I(1), causing anomalies in the transmission signal of the sample, especially when the sample edge jump is relatively small. To remedy this, Soller slits were constructed and placed between the foil and I(1) to minimize back-fluorescence from the foil. A comparison of blank and standard samples, measured with or without Soller slits or under a worst-case scenario, demonstrates the advantages of Soller slits when analyzing weak signal samples via transmission XAS.

  17. A new near-infrared absorption and fluorescent probe based on bombesin for molecular imaging

    NASA Astrophysics Data System (ADS)

    Kujala, Naresh; Zhai, Huifang; Smith, Charles; Prasanphanich, Adam; Sieckman, Gary; Hoffman, Timothy; Volkert, Wynn; Ma, Lixin; Yu, Ping

    2009-02-01

    We have developed a series of new dye bombesin conjugates for site-specific absorption and fluorescence imaging of human prostate and breast cancers. Bombesin (BBN), an amphibian analog to the endogenous ligand, binds to the gastrin releasing peptide (GRP) receptors with high specificity and affinity. Previously, we developed an Alexa Fluor 680-GGG-BBN peptide conjugate which demonstrated high binding affinity and specificity for breast cancer cells in the in vitro and in vivo tests (Ref: Ma et al., Molecular Imaging, vol. 6, no. 3, 2007: 171-180). This probe can not be used as an absorption probe in near-infrared imaging because its absorption peak is in the visible wavelength range. In addition, site specific longer wavelength fluorescent probe is desired for in vivo molecular imaging because long wavelength photons penetrate deeper into tissue. The new absorption and fluorescent probe we developed is based on the last eight-residues of BBN, -Q-W-A-V-G-H-L-M-(NH2), and labeled with AlexaFluor750 through a chemical linker, beta-alanine. The new probe, Alexa Fluor 750-BetaAla-BBN(7-14)NH2, exhibits optimal pharmacokinetics for specific targeting and optical imaging of the GRP receptor over-expressing cancer cells. Absorption spectrum has been measured and showed absorption peaks at 690nm, 720nm and 735nm. Fluorescent band is located at 755nm. In vitro and in vivo investigations have demonstrated the effectiveness of the new conjugates to specifically target human cancer cells overexpressing GRP receptors and tumor xenografts in severely compromised immunodeficient mouse model.

  18. 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.

  19. High-resolution fluorescence excitation spectra of jet-cooled benzyl and p-methylbenzyl radicals

    NASA Astrophysics Data System (ADS)

    Lin, Tai-Yuan David; Tan, Xue-Qing; Cerny, Timothy M.; Williamson, James M.; Cullin, David W.; Miller, Terry A.

    1992-11-01

    High-resolution, rotationally resolved, laser-induced, fluorescence excitation spectra of the A 1 and 6a 10 bands of benzyl and the 0 00 band of p-methylbenzyl radicals were obtained in supersonic expansions. All three spectra were assigned and fit, using the rigid rotor Hamiltonian as well as methyl group internal rotation theory. The results of the rotational analysis provide good rotation constants for benzyl and p-methylbenzyl and establish unambiguously that the symmetry of the excited electronic state in this transition of p-methylbenzyl is 2A 2 (in C 2v). The heights of torsional barriers that hinder the internal rotation of the methyl group in p-methylbenzyl also are determined. The torsional results are compared to those obtained previously for this radical in a vibrational analysis and to other open shell radicals.

  20. [Laser induced breakdown spectra of coal sample and self-absorption of the spectral line].

    PubMed

    Zhang, Gui-yin; Ji, Hui; Jin, Yi-dong

    2014-12-01

    The LIBS of one kind of household fuel coal was obtained with the first harmonic output 532 nm of an Nd·YAG laser as radiation source. With the assignment of the spectral lines, it was found that besides the elements C, Si, Mg, Fe, Al, Ca, Ti, Na and K, which are reported to be contained in coal, the presented sample also contains trace elements, such as Cd, Co, Hf, Ir, Li, Mn, Ni, Rb, Sr, V, W, Zn, Zr etc, but the spectral lines corresponding to O and H elements did not appear in the spectra. This is owing to the facts that the transition probability of H and O atoms is small and the energy of the upper level for transition is higher. The results of measurement also show that the intensity of spectral line increases with the laser pulse energy and self-absorption of the spectral lines K766.493 nm and K769.921 nm will appear to some extent. Increasing laser energy further will make self-absorption more obvious. The presence of self-absorption can be attributed to two factors. One is the higher transition rate of K atoms, and the other is that the increase in laser intensity induces the enhancement of the particle number density in the plasma.

  1. 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.

  2. 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.

  3. [Application of PARAFAC method and 3-D fluorescence spectra in petroleum pollutant measurement and analysis].

    PubMed

    Pan, Zhao; Wang, Yu-tian; Shao, Xiao-qing; Wu, Xi-jun; Yang, Li-li

    2012-03-01

    A method for identification and concentration measurement of petroleum pollutant by combining three-dimensional (3-D) fluorescence spectra with parallel factor analysis (PARAFAC) was proposed. The main emphasis of research was the measurement of coexisting different kinds of petroleum. The CCl4 solutions of a 0# diesel sample, a 97# gasoline sample, and a kerosene sample were used as measurement objects. The condition of multiple petroleum coexistence was simulated by petroleum solutions with different mixed ratios. The character of PARAFAC in complex mixture coexisting system analysis was studied. The spectra of three kinds of solutions and the spectra of gasoline-diesel mixed samples, diesel-kerosene mixed samples, and gas oline-diesel mixed with small counts of kerosene interference samples were analyzed respectively. The core consistency diagnostic method and residual sum of squares method were applied to calculate the number of factors in PARAFAC. In gasoline-diesel experiment, gasoline or diesel can be identified and measured as a whole respectively by 2-factors parallel factors analysis. In diesel-kerosene experiment, 2-factors parallel factors analysis can only obtain the characters of diesel, and the 3rd factor is needed to separate the kerosene spectral character from the mixture spectrum. When small counts of kerosene exist in gasoline-diesel solution, gasoline and diesel still can be identified and measured as principal components by a 2-factors parallel factor analysis, and the effect of interference on qualitative analysis is not significant. The experiment verified that the PARAFAC method can obtain characteristic spectrum of each kind of petroleum, and the concentration of petroleum in solutions can be predicted simultaneously, with recoveries shown in the paper. The results showed the possibility of petroleum pollutant identification and concentration measurement based on the 3-D fluorescence spectra and PARAFAC.

  4. 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.

  5. Charge transfer optical absorption and fluorescence emission of 4-(9-acridyl)julolidine from long-range-corrected time dependent density functional theory in polarizable continuum approach

    NASA Astrophysics Data System (ADS)

    Kityk, A. V.

    2014-07-01

    A long-range-corrected time-dependent density functional theory (LC-TDDFT) in combination with polarizable continuum model (PCM) have been applied to study charge transfer (CT) optical absorption and fluorescence emission energies basing on parameterized LC-BLYP xc-potential. The molecule of 4-(9-acridyl)julolidine selected for this study represents typical CT donor-acceptor dye with strongly solvent dependent optical absorption and fluorescence emission spectra. The result of calculations are compared with experimental spectra reported in the literature to derive an optimal value of the model screening parameter ω. The first absorption band appears to be quite well predictable within DFT/TDDFT/PCM with the screening parameter ω to be solvent independent (ω≈0.245 Bohr-1) whereas the fluorescence emission exhibits a strong dependence on the range separation with ω-value varying on a rising solvent polarity from about 0.225 to 0.151 Bohr-1. Dipolar properties of the initial state participating in the electronic transition have crucial impact on the effective screening.

  6. Recovering fluorescent spectra with an RGB digital camera and color filters using different matrix factorizations.

    PubMed

    Nieves, Juan L; Valero, Eva M; Hernández-Andrés, Javier; Romero, Javier

    2007-07-01

    The aim of a multispectral system is to recover a spectral function at each image pixel, but when a scene is digitally imaged under a light of unknown spectral power distribution (SPD), the image pixels give incomplete information about the spectral reflectances of objects in the scene. We have analyzed how accurately the spectra of artificial fluorescent light sources can be recovered with a digital CCD camera. The red-green-blue (RGB) sensor outputs are modified by the use of successive cutoff color filters. Four algorithms for simplifying the spectra datasets are used: nonnegative matrix factorization (NMF), independent component analysis (ICA), a direct pseudoinverse method, and principal component analysis (PCA). The algorithms are tested using both simulated data and data from a real RGB digital camera. The methods are compared in terms of the minimum rank of factorization and the number of sensors required to derive acceptable spectral and colorimetric SPD estimations; the PCA results are also given for the sake of comparison. The results show that all the algorithms surpass the PCA when a reduced number of sensors is used. The experimental results suggest a significant loss of quality when more than one color filter is used, which agrees with the previous results for reflectances. Nevertheless, an RGB digital camera with or without a prefilter is found to provide good spectral and colorimetric recovery of indoor fluorescent lighting and can be used for color correction without the need of a telespectroradiometer.

  7. Optical sensor instrumentation using absorption- and fluorescence-based capillary waveguide optrodes

    NASA Astrophysics Data System (ADS)

    Weigl, Bernhard H.; Draxler, Sonja; Kieslinger, Dietmar; Lehmann, H.; Trettnak, Wolfgang; Wolfbeis, Otto S.; Lippitsch, Max E.

    1995-09-01

    An analytical instrument comprising absorption- and fluorescence-based capillary waveguide optrodes (CWOs) is described. Glass capillaries with a chemically sensitive coating on the inner surface are used for optical chemical sensing in gaseous and liquid samples. In case of absorption-based CWOs, light from a LED is coupled into and out of the capillary under a defined angle via a rigid waveguide and an immersion coupler. The coated glass capillary forms an inhomogeneous waveguide, in which the light is guided in both the glass and the coating. The portion of the light which is absorbed in the chemically sensitive coating is proportional to a chemcial concentration or activity. This principle is demonstrated with a pCO2-sensitive inner coating. Typical relative light intensity signal changes with this type of optical interrogation are 98%, with an active capillary length of 10 mm. For fluorescence- based CWOs, the excitation light from an LED is coupled diffusely into the glass capillary and the optical sensor layer. A major portion of the excited fluorescence light is then collected within the coated capillary, and guided to the photodiode, which is located on the distal end of the capillary waveguide. Hereby, the excitation light is separated very efficiently from the fluorescent light. As an example, a CWO for pO2 is described. By applying this optical geometry, it was possible to utilize fluorescence decay time of the sensor layer as the transducer signal even when using solid state components (LEDs and photodiodes).

  8. Fluorescence and Raman spectra on surface of K9 glass by high fluence ultraviolet laser irradiation at 355 nm

    NASA Astrophysics Data System (ADS)

    Zhang, Zhen; Huang, Jin; Geng, Feng; Zhou, Xiaoyan; Feng, Shiquan; Ren, Dahua; Cheng, Xinlu; Jiang, Xiaodong; Wu, Weidong; Zheng, Wanguo; Tang, Yongjian

    2013-11-01

    In order to explore the damage mechanisms of K9 glass irradiated by high energy density ultraviolet laser, laser-induced fluorescence and Raman spectra were investigated. Compared the fluorescence spectra of damaged area, undamaged area and sub-damaged area, it can be conclude that the fluorescence spectrum of sub-damaged area is different from the structure of the other two areas. Especially, the main peak of the spectra at 415 nm reveals the unique characteristics of K9 glass. The structure at the sub-damaged area enhances intensity of the Raman scattering spectra. Three peaks of the spectra at about 500 nm and two characteristic peaks at about 550 nm exhibit the characterization of damaged area. A peak of the Raman scattering spectra at 350 nm which related to water can be observed. The relationship between intensity of Raman scattering and laser intensity at 355 nm is investigated by confocal Raman microscopy. At sub-damage area, signal of Raman scattering is rather high and decreased dramatically with respect to energy density. The major band at about 1470 cm-1 sharpened and moved to higher frequency with densification. These phenomena demonstrate that the structure of sub-damaged area has some characterization compared with the damaged area. The investigation of defect induced fluorescence and Raman spectra on surface of K9 glass is important to explore the damage mechanisms of optical materials irradiated by ultraviolet laser irradiation at 355 nm.

  9. 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.

  10. 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.

  11. Effect of Pressure on Absorption Spectra of Lycopene in n-Hexane and CS2 Solvents

    NASA Astrophysics Data System (ADS)

    Zhang, Wei; Liu, Wei-Long; Zheng, Zhi-Ren; Huo, Ming-Ming; Li, Ai-Hua; Yang, Bin

    2010-01-01

    The absorption spectra of lycopene in n-hexane and CS2 are measured under high pressure and the results are compared with β-carotene. In the lower pressure range, the deviation from the linear dependence on the Bayliss parameter (BP) for β-carotene is more visible than that for lycopene. With the further increase of the solvent BP, the 0-0 bands of lycopene and β-carotene red shift at almost the same rate in n-hexane; however, the 0-0 band of lycopene red shifts slower than that of β-carotene in CS2. The origins of these diversities are discussed taking into account the dispersion interactions and structures of solute and solvent molecules.

  12. Breaking of symmetrical charge distribution in xanthylocyanine chromophores detecting by their absorption spectra

    NASA Astrophysics Data System (ADS)

    Vasyluk, S. V.; Viniychuk, O. O.; Poronik, Ye. M.; Kovtun, Yu. P.; Shandura, M. P.; Yashchuk, V. M.; Kachkovsky, O. D.

    2011-03-01

    A detailed experimental investigation and quantum-chemical analysis of symmetrical cyanines with xanthylium and its substituted derivatives and with different polymethine chain (containing 1 and 2 vinylene groups) have been performed with the goal of understanding the nature of the electronic transitions in molecules. It is established electronic transitions in carbocyanines are similar to that in the typical Brooker's cyanines. In contrast, the absorption spectra of dicarbocyanines demonstrate a strong solvent dependence and substantial band broadening represented by the growth of the short wavelength shoulder. Basing on the results of the quantum-chemical calculation and conception of the mobile solitonic-like charge waves, we have concluded that the dicarbocyanines exist in two charged forms in the ground state with symmetrical and unsymmetrical distributions of the charge density. These are the examples of the cationic cyanines with the shortest chain when the symmetry breaking occurs.

  13. 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

  14. Comparison of absorption spectra of adenocarcinoma and squamous cell carcinoma cervical tissue

    NASA Astrophysics Data System (ADS)

    Peresunko, O. P.; Zelinska, N. V.; Prydij, O. G.; Zymnyakov, D. A.; Ushakova, O. V.

    2013-12-01

    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. Femtosecond Fluorescence Spectra of Tryptophan in Human γ-Crystallin Mutants: Site-Dependent Ultrafast Quenching

    PubMed Central

    Xu, Jianhua; Chen, Jiejin; Toptygin, Dmitri; Tcherkasskaya, Olga; Callis, Patrik; King, Jonathan; Brand, Ludwig; Knutson, Jay R.

    2012-01-01

    The eye lens crystallin proteins are subject to UV irradiation throughout life, and the photochemistry of damage proceeds through the excited state; thus, their tryptophan (Trp) fluorescence lifetimes are physiologically important properties. The time resolved fluorescence spectra of single Trps in human γD- and γS-crystallins have been measured with both an upconversion spectrophotofluorometer on the 300fs to 100ps time scale, and a time correlated single photon counting apparatus on the 100ps to 10ns time scale, respectively. Three Trps in each wild type protein were replaced by phenylalanine, leading to single-Trp mutants: W68-only and W156-only of HγD- and W72-only and W162-only of HγS-crystallin. These proteins exhibit similar ultrafast signatures: positive definite decay associated spectra (DAS) for 50 – 65ps decay constants that indicate dominance of fast, heterogeneous quenching. The quenched population (judged by amplitude) of this DAS differs among mutants. Trps 68, 156 in human γD- and Trp72 in human γS-crystallin are buried, but water can reach amide oxygen and ring HE1 atoms through narrow channels. QM-MM simulations of quenching by electron transfer predict heterogeneous decay times from 50–500 ps that agree with our experimental results. Further analysis of apparent radiative lifetimes allow us to deduce that substantial subpopulations of Trp are fully quenched in even faster (sub-300 fs) processes for several of the mutants. The quenching of Trp fluorescence of human γD- and γS-crystallin may protect them from ambient light induced photo damage. PMID:19919143

  16. Calculation of optical and K pre-edge absorption spectra for ferrous iron of distorted sites in oxide crystals

    NASA Astrophysics Data System (ADS)

    Vercamer, Vincent; Hunault, Myrtille O. J. Y.; Lelong, Gérald; Haverkort, Maurits W.; Calas, Georges; Arai, Yusuke; Hijiya, Hiroyuki; Paulatto, Lorenzo; Brouder, Christian; Arrio, Marie-Anne; Juhin, Amélie

    2016-12-01

    Advanced semiempirical calculations have been performed to compute simultaneously optical absorption and K pre-edge x-ray absorption spectra of Fe2 + in four distinct site symmetries found in minerals. The four symmetries, i.e., a distorted octahedron, a distorted tetrahedron, a square planar site, and a trigonal bipyramidal site, are representative of the Fe2 + sites found in crystals and glasses. A particular attention has been paid to the definition of the p -d hybridization Hamiltonian which occurs for noncentrosymmetric symmetries in order to account for electric dipole transitions. For the different sites under study, an excellent agreement between calculations and experiments was found for both optical and x-ray absorption spectra, in particular in terms of relative intensities and energy positions of electronic transitions. To our knowledge, these are the first calculations of optical absorption spectra on Fe2 + placed in such diverse site symmetries, including centrosymmetric sites. The proposed theoretical model should help to interpret the features of both the optical absorption and the K pre-edge absorption spectra of 3 d transition metal ions and to go beyond the usual fingerprint interpretation.

  17. 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.

  18. Mathematical model to interpret localized reflectance spectra measured in the presence of a strong fluorescence marker

    PubMed Central

    Bravo, Jaime J.; Davis, Scott C.; Roberts, David W.; Paulsen, Keith D.; Kanick, Stephen C.

    2016-01-01

    Abstract. 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. PMID:26836297

  19. 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.

  20. 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.

  1. Improved Savitzky-Golay-method-based fluorescence subtraction algorithm for rapid recovery of Raman spectra.

    PubMed

    Chen, Kun; Zhang, Hongyuan; Wei, Haoyun; Li, Yan

    2014-08-20

    In this paper, we propose an improved subtraction algorithm for rapid recovery of Raman spectra that can substantially reduce the computation time. This algorithm is based on an improved Savitzky-Golay (SG) iterative smoothing method, which involves two key novel approaches: (a) the use of the Gauss-Seidel method and (b) the introduction of a relaxation factor into the iterative procedure. By applying a novel successive relaxation (SG-SR) iterative method to the relaxation factor, additional improvement in the convergence speed over the standard Savitzky-Golay procedure is realized. The proposed improved algorithm (the RIA-SG-SR algorithm), which uses SG-SR-based iteration instead of Savitzky-Golay iteration, has been optimized and validated with a mathematically simulated Raman spectrum, as well as experimentally measured Raman spectra from non-biological and biological samples. The method results in a significant reduction in computing cost while yielding consistent rejection of fluorescence and noise for spectra with low signal-to-fluorescence ratios and varied baselines. In the simulation, RIA-SG-SR achieved 1 order of magnitude improvement in iteration number and 2 orders of magnitude improvement in computation time compared with the range-independent background-subtraction algorithm (RIA). Furthermore the computation time of the experimentally measured raw Raman spectrum processing from skin tissue decreased from 6.72 to 0.094 s. In general, the processing of the SG-SR method can be conducted within dozens of milliseconds, which can provide a real-time procedure in practical situations.

  2. Specific absorption spectra of hemoglobin at different PO2 levels: potential noninvasive method to detect PO2 in tissues.

    PubMed

    Liu, Peipei; Zhu, Zhirong; Zeng, Changchun; Nie, Guang

    2012-12-01

    Hemoglobin (Hb), as one of main components of blood, has a unique quaternary structure. Its release of oxygen is controlled by oxygen partial pressure (PO2). We investigate the specific spectroscopic changes in Hb under different PO2 levels to optimize clinical methods of measuring tissue PO2. The transmissivity of Hb under different PO2 levels is measured with a UV/Vis fiber optic spectrometer. Its plotted absorption spectral curve shows two high absorption peaks at 540 and 576 nm and an absorption valley at 560 nm when PO2 is higher than 100 mm Hg. The two high absorption peaks decrease gradually with a decrease in PO2, whereas the absorption valley at 560 nm increases. When PO2 decreases to approximately 0 mm Hg, the two high absorption peaks disappear completely, while the absorption valley has a hypochromic shift (8 to 10 nm) and forms a specific high absorption peak at approximately 550 nm. The same phenomena can be observed in visible reflectance spectra of finger-tip microcirculation. Specific changes in extinction coefficient and absorption spectra of Hb occur along with variations in PO2, which could be used to explain pathological changes caused by tissue hypoxia and for early detection of oxygen deficiency diseases in clinical monitoring.

  3. Specific absorption spectra of hemoglobin at different PO2 levels: potential noninvasive method to detect PO2 in tissues

    NASA Astrophysics Data System (ADS)

    Liu, Peipei; Zhu, Zhirong; Zeng, Changchun; Nie, Guang

    2012-12-01

    Hemoglobin (Hb), as one of main components of blood, has a unique quaternary structure. Its release of oxygen is controlled by oxygen partial pressure (PO2). We investigate the specific spectroscopic changes in Hb under different PO2 levels to optimize clinical methods of measuring tissue PO2. The transmissivity of Hb under different PO2 levels is measured with a UV/Vis fiber optic spectrometer. Its plotted absorption spectral curve shows two high absorption peaks at 540 and 576 nm and an absorption valley at 560 nm when PO2 is higher than 100 mm Hg. The two high absorption peaks decrease gradually with a decrease in PO2, whereas the absorption valley at 560 nm increases. When PO2 decreases to approximately 0 mm Hg, the two high absorption peaks disappear completely, while the absorption valley has a hypochromic shift (8 to 10 nm) and forms a specific high absorption peak at approximately 550 nm. The same phenomena can be observed in visible reflectance spectra of finger-tip microcirculation. Specific changes in extinction coefficient and absorption spectra of Hb occur along with variations in PO2, which could be used to explain pathological changes caused by tissue hypoxia and for early detection of oxygen deficiency diseases in clinical monitoring.

  4. 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.

  5. 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.

  6. Signatures in vibrational and UV-visible absorption spectra for identifying cyclic hydrocarbons by graphene fragments.

    PubMed

    Meng, Yan; Wu, Qi; Chen, Lei; Wangmo, Sonam; Gao, Yang; Wang, Zhigang; Zhang, Rui-Qin; Ding, Dajun; Niehaus, Thomas A; Frauenheim, Thomas

    2013-12-21

    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.

  7. Polarized absorption spectra of single crystals of lunar pyroxenes and olivines.

    NASA Technical Reports Server (NTRS)

    Burns, R. G.; Huggins, F. E.; Abu-Eid, R. M.

    1972-01-01

    Measurements have been made of the polarized absorption spectra (360-2200 nm) of compositionally zoned pyroxene minerals in rocks 10045, 10047 and 10058 and olivines in rocks 10020 and 10022. The Apollo 11 pyroxenes with relatively high Ti/Fe ratios were chosen initially to investigate the presence of crystal field spectra of Fe(2+) and Ti(3+) ions in the minerals. Broad intense bands at about 1000 and 2100 nm arise from spin-allowed, polarization-dependent transitions in Fe(2+) ions in pyroxenes. Several weak sharp peaks occur in the visible region. Peaks at 402, 425, 505, 550, and 585 nm represent spin-forbidden transitions in Fe(2+) ions, while broader bands at 460-470 nm and 650-660 nm are attributed to Ti(3+) ions. Charge transfer bands, which in terrestrial pyroxenes often extend into the visible region, are displaced to shorter wavelengths in lunar pyroxenes. This feature correlates with the absence of Ti(3+) ions in these minerals.

  8. Progress in the Theory and Interpretation of X-ray Absorption Spectra

    NASA Astrophysics Data System (ADS)

    Rehr, J. J.

    2002-03-01

    There has been dramatic progress in recent years in the understanding of x-ray absorption spectra (XAS) [1]. For example, modern real space multiple scattering theory has yielded a quantitative treatment of the extended fine structure in XAS. Crucial in the theory is a treatment of electronic excited states including many-body effects such as inelastic losses and Debye-Waller factors. These developments have led to ab initio codes which permit an interpretation of the spectra in terms of geometrical and electronic properties of materials [2]. Indeed, the availability of such codes has revolutionized experimental investigations based on synchrotron radiation x-ray sources. Algorithmic improvements have recently made possible fast, parallel calculations of the near edge structure (XANES) [3], and approximate treatments of local field effects and many-body amplitude factors. Related techniques have been applied to several other spectroscopies, e.g., anomalous x-ray scattering, x-ray magnetic circular dichroism, and photoelectron diffraction [4]. [1] J. J. Rehr and R. C. Albers, Rev. Mod. Phys. 72, 621 (2000); [2] A. L. Ankudinov, B. Ravel, J.J. Rehr, and S. Conradson, Phys. Rev. B 58, 7565 (1998); [3] A. L. Ankudinov, C. E. Bouldin, J. J. Rehr, J. Sims, and H. Hung, Phys. Rev. B, in press (2002); [4] F. J. Garcia de Abajo, M. A. Van Hove, C. S. Fadley, Phys. Rev. B 63, 075404 (2001).

  9. C-13 NMR chemical shifts and visible absorption spectra of unsymmetrical fluoran dye by MO calculations

    NASA Astrophysics Data System (ADS)

    Hoshiba, T.; Ida, T.; Mizuno, M.; Otsuka, T.; Takaoka, K.; Endo, K.

    2002-01-01

    An unsymmetrical fluoran dye, 3-diethylamino-6-methyl-7-chlorofluoran (DEAMCF) is one of the leuco dyes which shows the coloring-to-decoloring reversible reaction with acidity. We calculated the 13C chemical shieldings of the DEAMCF with the frame model compounds using ab initio gauge invariant atomic orbital methods, and compared it with the experimental shifts. The calculated values of the frame compounds are in good agreement with the experimental ones in the error range of -4.9-16.7 ppm. The calculated ones for the decolored-form of the DEAMCF reflected the observed ones, although the errors range from -13.4 to 23.1 ppm. Furthermore, we analyzed the UV-Visible absorption spectra of the decolored and colored forms of DEAMCF by a semiempirical ZINDO MO method. For the colored form, the observed absorption peaks at 550 and 510 nm correspond to the excitation from π-bonding HOMO (π-electrons which conjugated in xanthene ring) and π-bonding nearest HOMO (π-electrons concentrated in benzene-ring with methyl and Cl groups of xanthene) to π ∗-antibonding LUMO (π ∗-electrons of xanthene), respectively.

  10. Ultraviolet spectra of quenched carbonaceous composite derivatives: Comparison to the '217 nanometer' interstellar absorption feature

    NASA Technical Reports Server (NTRS)

    Sakata, Akira; Wada, Setsuko; Tokunaga, Alan T.; Narisawa, Takatoshi; Nakagawa, Hidehiro; Ono, Hiroshi

    1994-01-01

    QCCs (quenched carbonaceous composite) are amorphus carbonaceous material formed from a hydrocarbon plasma. We present the UV-visible spectra of 'filmy QCC; (obtained outside of the beam ejected from the hydrocarbon plasma) and 'dark QCC' (obtained very near to the beam) for comparison to the stellar extinction curve. When filmy QCC is heated to 500-700 C (thermally altered), the wavelength of the absorption maximum increases form 204 nm to 220-222 nm. The dark QCC has an absorption maximum at 217-222 nm. In addition, the thermally altered filmy QCC has a slope change at about 500 nm which resmbles that in the interstellar extinction curve. The resemblance of the extinction curve of the QCCs to that of the interstellar medium suggests that QCC derivatives may be representative of the type of interstellar material that produces the 217 nm interstellar medium feature. The peak extinction of the dark QCC is higher than the average interstellar extinction curve while that of the thermally altered filmy QCC is lower, so that a mixture of dark and thermally altered filmy QCC can match the peak extinction observed in the interstellar medium. It is shown from electron micrographs that most of the thermally altered flimy QCC is in the form of small grainy structure less than 4 nm in diameter. This shows that the structure unit causing the 217-222 nm feature in QCC is very small.

  11. A combination spectrophotometer for measuring electronic absorption, natural circular dichroism, and magnetic circular dichroism spectra

    NASA Astrophysics Data System (ADS)

    Policke, Timothy A.; Schreiner, Anton F.; Trexler, Jack W.; Knopp, James A.

    1990-08-01

    The design, construction, and evaluation of a combination spectrometer for measuring electronic absorption (EA), natural circular dichroism (CD), and magnetic circular dichroism (MCD) are described. Around the optical components of a JASCO ORD/UV-5 spectropolarimeter, a new EA/CD/MCD instrument was built with the realized intentions of increasing sensitivity and upgrading the analog tube type circuitry to a solid-state digitally, computer-controlled spectrophotometer. It is a flexible, dynamic, and user-controllable system, interfaced to an Apple II Plus computer, for studying instrument and signal parameters. The monochromator (M), photoelastic modulator (PEM), photomultiplier tube applied voltage (PMHV), and photomultiplier tube dc output current (PMdc) are under complete and independent software control. Our system has two unique aspects for obtaining the circular dichroism. First, the ac signal is measured with a voltage-to-frequency (V/f) converter; and, second, both the ac and the dc are independently recorded and their ratio is digitally calculated. This design has several advantages which include the elimination of voltage divider integrated circuits or division electronics, a wide dynamic range, a greater precision of ac values at low percentages of full scale, and the capability of continuous integration over long time periods. Also, both types of spectra, EA and CD or MCD, are obtained from the current output of the PM. This paper not only describes the design of the instrument for obtaining the two types of spectra but also compares four methods of obtaining the circular dichroism. Sensitivities of ˜1×10-7ΔA units are achievable as determined by measuring CD spectra of the well-known enantiomer (+)-[Co(en)3]3+.

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

    NASA Astrophysics Data System (ADS)

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

    2013-05-01

    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.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. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr00308f

  13. 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.

  14. A mixed quantum-classical description of pheophorbide a linear absorption spectra: Quantum-corrections of the Qy- and Qx-absorption vibrational satellites

    NASA Astrophysics Data System (ADS)

    Megow, Jörg; Kulesza, Alexander; May, Volkhard

    2016-01-01

    The ground-state classical path approximation is utilized to compute molecular absorption spectra in a mixed quantum-classical frame. To improve the description for high-frequency vibrational satellites, related quantum correction factors are introduced. The improved method is demonstrated for the Qy- and Qx-bands of pheophorbide a.

  15. Soft X-ray absorption spectra in the 0 K region of microporous carbon and some reference aromatic compounds

    SciTech Connect

    Muramatsu, Yasuji; Kuramoto, Kentaro; Gullikson, Eric M.; Perera, Rupert C.C.

    2003-06-01

    To analyze the oxidation states of the graphitic surface of microporous carbon, soft X-ray absorption spectra in the 0 K region have been obtained for microporous carbon and various aromatic compounds. The aromatic molecules studied are substituted with one or more of the following oxygenated functional groups: hydroxy (-OH), carboxy (-COOH), carbonyl (>C=O), formyl (-CH=O), and ether (-O-). From comparison of the soft X-ray absorption spectra of microporous carbon and of reference aromatic compounds, the most probable chemical bonding states of oxygen in microporous carbon are found to be -COOH and >C(H)=O. Spectral features in the soft X-ray absorption spectra of microporous carbon are well explained by the O2p density of states in these oxygenated functional groups from discrete variational (DV)-X{alpha} molecular orbital calculations.

  16. [Two-photon excitation fluorescence spectrum of the light-harvesting complex LH2 from Chromatium minutissimum within 650-745 nm range is determined by two-photon absorption of bacteriochlorophyll rather than of carotenoids].

    PubMed

    Krikunova, M A; Leupold, D; Rini, M; Voigt, B; Moskalenko, A A; Toropygina, O A; Razzhivin, A P

    2002-01-01

    Two-photon fluorescence excitation spectra of the peripheral light-harvesting complex LH2 from the purple photosynthetic bacterium Chromatium minutissimum were examined within the expected spectral range of the optically forbidden S1 singlet state of carotenoids. LH2 preparations isolated from wild-type and carotenoid-depleted cells were used. 100-fs laser pulses in the range of 1300-1490 nm with an energy of 7-9 mW (corresponding to one-photon absorption between 650 and 745 nm) were used for two-photon fluorescence excitation. It was shown that two-photon fluorescence excitation spectra of LH2 complex from wild and carotenoid-depleted cells are very similar to each other and to the two-photon fluorescence excitation spectrum of bacteriochlorophyll a in acetone. It was concluded that direct two-photon excitation of bacteriochlorophyll a determines the fluorescence of both samples within the 650-745 nm spectral range.

  17. 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.

  18. Reverse engineering a spectrum: using fluorescent spectra of molecular hydrogen to recreate the missing Lyman-α line of pre-main sequence stars

    NASA Astrophysics Data System (ADS)

    Linsky, J. L.; Herczeg, G.; Wood, B. E.

    2008-12-01

    The hydrogen Lyman-α (Lyα) line, a major source of ionization of metals in the circumstellar disks of pre-main sequence (PMS) stars, is usually not observed due to absorption by interstellar and circumstellar hydrogen. We have developed a technique to reconstruct the intrinsic Lyα line using the observed emission in the H2 B-X lines that are fluoresced by Lyα. We describe this technique and the subsequent analysis of the ultraviolet (UV) spectra of the TW Hya, RU Lupi and other PMS stars. We find that the reconstructed Lyα lines are indeed far brighter than any other feature in the UV spectra of these stars and therefore play an important role in the ionization and heating of the outer layers of circumstellar disks.

  19. Donor-acceptor substituted phenylethynyltriphenylenes – excited state intramolecular charge transfer, solvatochromic absorption and fluorescence emission

    PubMed Central

    Nandy, Ritesh

    2010-01-01

    Summary Several 2-(phenylethynyl)triphenylene derivatives bearing electron donor and acceptor substituents on the phenyl rings have been synthesized. The absorption and fluorescence emission properties of these molecules have been studied in solvents of different polarity. For a given derivative, solvent polarity had minimal effect on the absorption maxima. However, for a given solvent the absorption maxima red shifted with increasing conjugation of the substituent. The fluorescence emission of these derivatives was very sensitive to solvent polarity. In the presence of strongly electron withdrawing (–CN) and strongly electron donating (–NMe2) substituents large Stokes shifts (up to 130 nm, 7828 cm−1) were observed in DMSO. In the presence of carbonyl substituents (–COMe and –COPh), the largest Stokes shift (140 nm, 8163 cm−1) was observed in ethanol. Linear correlation was observed for the Stokes shifts in a Lippert–Mataga plot. Linear correlation of Stokes shift was also observed with E T(30) scale for protic and aprotic solvents but with different slopes. These results indicate that the fluorescence emission arises from excited state intramolecular charge transfer in these molecules where the triphenylene chromophore acts either as a donor or as an acceptor depending upon the nature of the substituent on the phenyl ring. HOMO–LUMO energy gaps have been estimated from the electrochemical and spectral data for these derivatives. The HOMO and LUMO surfaces were obtained from DFT calculations. PMID:21085512

  20. X-ray absorption and soft x-ray fluorescence analysis of KDP optics

    SciTech Connect

    Nelson, A J; van Buuren, T; Miller, E; Land, T A; Bostedt, C; Franco, N; Whitman, P K; Baisden, P A; Terminello, L J; Callcott, T A

    2000-08-09

    Potassium Dihydrogen Phosphate (KDP) is a non-linear optical material used for laser frequency conversion and optical switches. Unfortunately, when KDP crystals are coated with a porous silica anti-reflection coating [1] and then exposed to ambient humidity, they develop dissolution pits [2,3]. Previous investigations [2] have shown that thermal annealing renders KDP optics less susceptible to pitting suggesting that a modification of surface chemistry has occurred. X-ray absorption and fluorescence were used to characterize changes in the composition and structure of KDP optics as a function of process parameters. KDP native crystals were also analyzed to provide a standard basis for interpretation. Surface sensitive total electron yield and bulk sensitive fluorescence yield from the K 2p, P 2p (L{sub 2,3}-edge) and O 1s (K-edge) absorption edges were measured at each process step. Soft X-ray fluorescence was also used to observe changes associated with spectral differences noted in the absorption measurements. Results indicate that annealing at 160 C dehydrates the surface of KDP resulting in a metaphosphate surface composition with K:P:O = 1:1:3.

  1. 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.

  2. 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.

  3. 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.

  4. [Characteristics of the absorption spectra of the mixtures of C42(Al), C32 (Si) and so on].

    PubMed

    Chen, W

    1998-12-01

    The mixtures containing C42 (A1), C32 (Si), C30 (Ca) and C28 (Fe) are produced by means of arc discharge and He gas convection. The spectra are measured and compared with the absorption spectra of all carbon molecules. The result shows that after imbeded in all carbon molecules, the Al, Si, Ca and Fe atoms do not change the positions of the absorption peak of original molecules, but only change the probability of pi --> pi* transition and n --> pi* transition of these molecules.

  5. 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.

  6. Polarized fluorescence and absorption of macroscopically aligned Light Harvesting Complex II.

    PubMed

    van Amerongen, H; Kwa, S L; van Bolhuis, B M; van Grondelle, R

    1994-08-01

    Polarized absorption and fluorescence measurements have been performed at 77 K on isotropic and anisotropic preparations of trimeric Light Harvesting Complex II (LHC-II) from spinach. The results enable a decomposition of the absorption spectrum into components parallel and perpendicular to the trimeric plane. For the first time, it is shown quantitatively that the strong absorption band around 676 nm is polarized essentially parallel to the plane of the trimer, i.e., the average angle between the corresponding transition dipole moments and this plane is at most 12 degrees. The different absorption bands for LHC-II should not be considered as corresponding to individual pigments but to collective excitations of different pigments. Nevertheless, the average angle between the Qy transition dipole moments of all chlorophyll a pigments in LHC-II and the trimeric plane could be determined and was found to be 17.5 degrees +/- 2.5 degrees. For the chlorophyll b pigments, this angle is significantly larger (close to 35 degrees). At 77 K, most of the fluorescence stems from a weak band above 676 nm and the corresponding transition dipole moments are oriented further out of plane than the dipole moments corresponding to the 676-nm band. The results are shown to be of crucial significance for understanding the relation between the LHC-II structure and its spectroscopy.

  7. A theoretical investigation of the effect of water on the structure and fluorescence spectra of L-tryptophan

    NASA Astrophysics Data System (ADS)

    Ten, G. N.; Glukhova, O. E.; Slepchenkov, M. M.; Shcherbakova, N. E.; Baranov, V. I.

    2016-10-01

    Fluorescence spectra of two long-wavelength electron transitions S 0 ← 1 L b and S 0 ← 1 L a in uncharged and zwitterionic forms of L-tryptophan (Trp) in aqueous solution and in the complex of Trp with water molecule were calculated using the Frank-Condon approximation. Geometric parameters of Trp in electronically excited states were determined, and the vibrational structure of vibronic spectra was analyzed. It was shown that the relative position of structural fragments of alanine (R-Ala) and indole (R-In) could have a determining effect on the fluorescence and formation of the vibrational structure of electronic spectra. The increase of the rotation angle between the R-Ala and R-In, which depends on the Trp environment, results in the Trp fluorescence originating only from the singlet excited state 1 L a .

  8. Excitation and propagation of X-ray fluorescence through thin devices with hollowed ordered structures: comparison of experimental and theoretical spectra.

    PubMed

    Mazuritskiy, M I; Dabagov, S B; Marcelli, A; Lerer, A M; Dziedzic-Kocurek, K

    2016-01-01

    The lack of models describing the propagation of X-rays in waveguides and the interference mechanism between incident and reflected radiation waves hamper the understanding and the control of wave propagation phenomena occurring in many real systems. Here, experimental spectra collected at the exit of microchannel plates (MCPs) under the total X-ray reflection condition are presented. The results are discussed in the framework of a theoretical model in which the wave propagation is enhanced by the presence of a transition layer at the surface. The angular distributions of the propagating radiation at the exit of these MCPs with microchannels of ∼3 µm diameter will also be presented and discussed. These spectra show contributions associated with the reflection of the primary monochromatic beam and with the fluorescence radiation originating from the excitation of atoms composing the surface of the microchannel. The soft X-ray fluorescence spectra collected at the exit of microcapillaries were analyzed in the framework of a wave approximation while diffraction contributions observed at the exit of these hollow X-ray waveguides have been calculated using the Fraunhofer diffraction model for waves in the far-field domain. Data collected at the Si L-edge show that in glassy MCPs the fluorescence radiation can be detected only when the energy of the primary monochromatic radiation is above the absorption edge for grazing angles higher than half of the critical angle of the total reflection phenomenon. Experimental data and simulations of the propagating radiation represent a clear experimental confirmation of the channeling phenomenon of the excited fluorescence radiation inside a medium and point out that a high transmission can be obtained in waveguide optics for parameters relevant to X-ray imaging.

  9. Hydroxylated fluorescent dyes for live cell labeling: synthesis, spectra and superresolution STED** microscopy.

    PubMed

    Belov, Vladimir N; Butkevich, Alexey N; Kolmakov, Kirill; Sokolov, Viktor V; Shojaei, Heydar; Sidenstein, Sven C; Kamin, Dirk; Matthias, Jessica; Vlijm, Rifka; Engelhardt, Johann; Hell, Stefan W

    2017-03-29

    Hydroxylated rhodamines, carbopyronines, silico- and germanorhodamines with absorption maxima in the range of 530-640 nm were prepared and applied in specific labeling of living cells. The direct and high-yielding entry to germa- and silaxanthones tolerates the presence of protected heteroatoms and may be considered for the syntheses of various sila- and germafluoresceins, as well as -rhodols. Application in stimulated emission depletion (STED) fluorescence microscopy revealed a resolution of 50-75 nm in one- and two-color imaging of vimentin-HaloTag fused protein and native tubulin. The established structure-property relationships allow prediction of the spectral properties and the positions of spirolactone/zwitterion equilibria for the new analogs of rhodamines, carbo-, silico- and germanorhodamines using simple additive schemes.

  10. 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.

  11. 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.

  12. Absorption spectra of garnet films between 1. 0 and 1. 8. mu. m by guided-wave optical spectroscopy

    SciTech Connect

    Olivier, M.; Peuzin, J.; Danel, J.; Challeton, D.

    1981-01-15

    Continuous recording of the absorption spectra of thin films by an optical guided-wave technique is demonstrated. In the case of a garnet thin film of compositoin (YSmLuCa)/sub 3/(FeGe)/sub 5/O/sub 12/ it is shown that the near-infrared Sm/sup 3 +/ absorption bands are clearly visible in contrast with conventional transmission measurement. Comparison with the absorption spectrum of bulk Sm/sub 3/Fe/sub 5/O/sub 12/ garnet allows the determination of an Sm concentration in the film.

  13. Diagnosis of liver cancer and cirrhosis by the fluorescence spectra of blood and urine.

    PubMed

    AlSalhi, M; Al Mehmadi, A M; Abdo, Ayman Assad; Prasad, S; Masilamani, V

    2012-08-01

    Liver cancer or hepato cellular carcinoma (HCC) is a serious malady with only 10% survival rate and is fatal next only to pancreatic cancer. This disease is conventionally detected and diagnosed by ultra sound, CT or MRI scans which are quite expensive. Also the discrimination between cirrhosis and HCC, by these imaging techniques, is poor. The conventional tissue biopsy is quite invasive and painful. In the new diagnostic procedure presented in this paper we have obtained fluorescence emission spectra with excitation at 400 nm and the synchronous emission spectra (Δλ = 10 nm) for a set of blood and urine samples (Normal control N = 25, Liver Malfunction N = 58). Based on the ratio fluorometric parameters, all the three liver maladies (minor inflammation like Hepatitis C, serious diseases like Cirrhosis and hepatoma) could be detected and discriminated with an accuracy of about 80%. Hence this inexpensive, non invasive, optical technique may have significant impact in screening, diagnosis and also prognosis of HCC in large segment of people in the populous Asian countries.

  14. Absorption into fluorescence. A method to sense biologically relevant gas molecules

    NASA Astrophysics Data System (ADS)

    Strianese, Maria; Varriale, Antonio; Staiano, Maria; Pellecchia, Claudio; D'Auria, Sabato

    2011-01-01

    In this work we present an innovative optical sensing methodology based on the use of biomolecules as molecular gating nano-systems. Here, as an example, we report on the detection ofanalytes related to climate change. In particular, we focused our attention on the detection ofnitric oxide (NO) and oxygen (O2). Our methodology builds on the possibility of modulating the excitation intensity of a fluorescent probe used as a transducer and a sensor molecule whose absorption is strongly affected by the binding of an analyte of interest used as a filter. The two simple conditions that have to be fulfilled for the method to work are: (a) the absorption spectrum of the sensor placed inside the cuvette, and acting as the recognition element for the analyte of interest, should strongly change upon the binding of the analyte and (b) the fluorescence dye transducer should exhibit an excitation band which overlaps with one or more absorption bands of the sensor. The absorption band of the sensor affected by the binding of the specific analyte should overlap with the excitation band of the transducer. The high sensitivity of fluorescence detection combined with the use of proteins as highly selective sensors makes this method a powerful basis for the development of a new generation of analytical assays. Proof-of-principle results showing that cytochrome c peroxidase (CcP) for NO detection and myoglobin (Mb) for O2 detection can be successfully used by exploiting our new methodology are reported. The proposed technology can be easily expanded to the determination of different target analytes.

  15. Absorption into fluorescence. A method to sense biologically relevant gas molecules.

    PubMed

    Strianese, Maria; Varriale, Antonio; Staiano, Maria; Pellecchia, Claudio; D'Auria, Sabato

    2011-01-01

    In this work we present an innovative optical sensing methodology based on the use of biomolecules as molecular gating nano-systems. Here, as an example, we report on the detection of analytes related to climate change. In particular, we focused our attention on the detection of nitric oxide (NO) and oxygen (O2). Our methodology builds on the possibility of modulating the excitation intensity of a fluorescent probe used as a transducer and a sensor molecule whose absorption is strongly affected by the binding of an analyte of interest used as a filter. The two simple conditions that have to be fulfilled for the method to work are: (a) the absorption spectrum of the sensor placed inside the cuvette, and acting as the recognition element for the analyte of interest, should strongly change upon the binding of the analyte and (b) the fluorescence dye transducer should exhibit an excitation band which overlaps with one or more absorption bands of the sensor. The absorption band of the sensor affected by the binding of the specific analyte should overlap with the excitation band of the transducer. The high sensitivity of fluorescence detection combined with the use of proteins as highly selective sensors makes this method a powerful basis for the development of a new generation of analytical assays. Proof-of-principle results showing that cytochrome c peroxidase (CcP) for NO detection and myoglobin (Mb) for O2 detection can be successfully used by exploiting our new methodology are reported. The proposed technology can be easily expanded to the determination of different target analytes.

  16. 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.

  17. Analysis of atmospheric trace constituents from high resolution infrared balloon-borne and ground-based solar absorption spectra

    NASA Technical Reports Server (NTRS)

    Goldman, A.; Murcray, F. J.; Rinsland, C. P.; Blatherwick, R. D.; Murcray, F. H.; Murcray, D. G.

    1991-01-01

    Results of ongoing studies of high-resolution solar absorption spectra aimed at the identification and quantification of trace constituents of importance in the chemistry of the stratosphere and upper troposphere are presented. An analysis of balloon-borne and ground-based spectra obtained at 0.0025/cm covering the 700-2200/cm interval is presented. The 0.0025/cm spectra, along with corresponding laboratory spectra, improves the spectral line parameters, and thus the accuracy of quantifying trace constituents. Results for COF2, F22, SF6, and other species are presented. The retrieval methods used for total column density and altitude distribution for both ground-based and balloon-borne spectra are also discussed.

  18. 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.

  19. Solvent effect on the absorption spectra of coumarin 120 in water: A combined quantum mechanical and molecular mechanical study.

    PubMed

    Sakata, Tetsuya; Kawashima, Yukio; Nakano, Haruyuki

    2011-01-07

    The solvent effect on the absorption spectra of coumarin 120 (C120) in water was studied utilizing the combined quantum mechanical∕molecular mechanical (QM∕MM) method. In molecular dynamics (MD) simulation, a new sampling scheme was introduced to provide enough samples for both solute and solvent molecules to obtain the average physical properties of the molecules in solution. We sampled the structure of the solute and solvent molecules separately. First, we executed a QM∕MM MD simulation, where we sampled the solute molecule in solution. Next, we chose random solute structures from this simulation and performed classical MD simulation for each chosen solute structure with its geometry fixed. This new scheme allowed us to sample the solute molecule quantum mechanically and sample many solvent structures classically. Excitation energy calculations using the selected samples were carried out by the generalized multiconfigurational perturbation theory. We succeeded in constructing the absorption spectra and realizing the red shift of the absorption spectra found in polar solvents. To understand the motion of C120 in water, we carried out principal component analysis and found that the motion of the methyl group made the largest contribution and the motion of the amino group the second largest. The solvent effect on the absorption spectrum was studied by decomposing it in two components: the effect from the distortion of the solute molecule and the field effect from the solvent molecules. The solvent effect from the solvent molecules shows large contribution to the solvent shift of the peak of the absorption spectrum, while the solvent effect from the solute molecule shows no contribution. The solvent effect from the solute molecule mainly contributes to the broadening of the absorption spectrum. In the solvent effect, the variation in C-C bond length has the largest contribution on the absorption spectrum from the solute molecule. For the solvent effect on the

  20. Finite temperature effects on the X-ray absorption spectra of energy related materials

    NASA Astrophysics Data System (ADS)

    Pascal, Tod; Prendergast, David

    2014-03-01

    We elucidate the role of room-temperature-induced instantaneous structural distortions in the Li K-edge X-ray absorption spectra (XAS) of crystalline LiF, Li2SO4, Li2O, Li3N and Li2CO3 using high resolution X-ray Raman spectroscopy (XRS) measurements and first-principles density functional theory calculations within the eXcited electron and Core Hole (XCH) approach. Based on thermodynamic sampling via ab-initio molecular dynamics (MD) simulations, we find calculated XAS in much better agreement with experiment than those computed using the rigid crystal structure alone. We show that local instantaneous distortion of the atomic lattice perturbs the symmetry of the Li 1 s core-excited-state electronic structure, broadening spectral line-shapes and, in some cases, producing additional spectral features. This work was conducted within the Batteries for Advanced Transportation Technologies (BATT) Program, supported by the U.S. Department of Energy Vehicle Technologies Program under Contract No. DE-AC02-05CH11231.

  1. Modeling of IR absorption spectra of the mixture CO2-He at moderate and high pressures

    NASA Astrophysics Data System (ADS)

    Golovko, Vladimir F.

    2004-02-01

    The He-broadened spectra of carbon dioxide are calculated within the pressure range 2-800 atm in the absorption regions of the bands v2, v3, and 3v3 that are positioned from 590 to 7020 cm-1. The main difficulty is consideration of the line shape narrowing at relatively high pressures. For Q-branches, this effect is observed at atmospheric conditions and, therefore, it is important for remote sounding of the gas atmosphere. The mixtures of the mentioned gases are well studied in experiments and it can serve as a good test for validating the simulating techniques developing. The line by line method is used with modeling of the single line shape without the conventional interference of lines. The problem is focused on the order and disorder in arrangement of the rotational lines with P-, R-, and Q-branches of vibrational bands. A database CDSD-1000 in the HITRAN format is reformatted with adding supplement four parameters for every entry. The physical meaning of the phenomena known as the line and branch mixing is discussed.

  2. Simulation of X-ray absorption spectra with orthogonality constrained density functional theory.

    PubMed

    Derricotte, Wallace D; Evangelista, Francesco A

    2015-06-14

    Orthogonality constrained density functional theory (OCDFT) [F. A. Evangelista, P. Shushkov and J. C. Tully, J. Phys. Chem. A, 2013, 117, 7378] 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.

  3. Dielectronic Recombination Of Iron M-shell Ions Motivated By Absorption Features In AGN Spectra

    NASA Astrophysics Data System (ADS)

    Lukic, Dragan; Schnell, M.; Savin, D. W.; Brandau, C.; Schmidt, E. W.; Yu, D.; Bernhardt, D.; Schippers, S.; Müller, A.; Lestinsky, M.; Orlov, D.; Sprenger, F.; Grieser, M.; Repnow, R.; Hoffmann, J.; Wolf, A.

    2006-09-01

    XMM-Newton and Chandra observations of active galactic nuclei (AGN) show spectra rich with X-ray absorption features. These observations have detected a broad unresolved transition array (UTA) between 15-17 Å. This is attributed to inner-shell photoexcitation of M-shell iron ions. Modeling these UTA features is currently limited by uncertainties in the low-temperature dielectronic recombination (DR) data for M-shell iron. In order to resolve this issue, and to provide reliable iron M-shell DR data for plasma modeling, we are carrying out a series of laboratory measurements using the heavy-ion Test Storage Ring (TSR) at the Max-Plank-Institute for Nuclear Physics in Heidelberg, Germany. We use the DR data obtained at TSR, to calculate rate coefficients for plasma modeling. We are also providing our data to atomic theorist to benchmark their DR calculations. Here we report our recent experimental results for DR for several iron M-shell ions and plans for future work. This work has been supported in part by NASA, the German Federal Ministry for Education and Research, and the German Research Council

  4. Free-energy predictions and absorption spectra calculations for supramolecular nanocarriers and their photoactive cargo.

    PubMed

    Pietropaolo, Adriana; Tang, Sicheng; Raymo, Françisco M

    2017-04-13

    We reconstructed the free-energy landscape for supramolecular nanoparticles of amphiphilic methacrylated-based co-polymers. Their self-assembly in aqueous solution and encapsulation of borondipyrromethene (BODIPY) derivatives were enforced through atomistic free-energy simulations. The BODIPY binding modes detected in each of the free-energy basins were validated through a comparison of theoretical absorption spectra, calculated at the TD-DFT level, to their experimental counterparts. The nanoparticle distribution is controlled within a thermodynamic regime, with free-energy barriers approaching 8 kcal mol(-1), enabling the existence of different-sized nanoparticles in aqueous solution at room temperature. Two types of supramolecular morphologies were identified. One is compact and spherical in shape and the other is large and donut-like, with the former more stable than the latter by 4 kcal mol(-1). The morphology of the supramolecular host affects the binding mode of the BODIPY guests. Stacked BODIPY aggregates are encapsulated in the spherical nanocarriers, whereas isolated chromophores associate with the donut-shaped assemblies.

  5. Calibration-free absolute quantification of optical absorption coefficients using acoustic spectra in 3D photoacoustic microscopy of biological tissue.

    PubMed

    Guo, Zijian; Hu, Song; Wang, Lihong V

    2010-06-15

    Optical absorption is closely associated with many physiological important parameters, such as the concentration and oxygen saturation of hemoglobin, and it can be used to quantify the concentrations of nonfluorescent molecules. We propose a method to use acoustic spectra of photoacoustic signals to quantify the absolute optical absorption. This method is self-calibrating and thus insensitive to variations in the optical fluence. Factors such as system bandwidth and acoustic attenuation can affect the quantification but can be canceled by dividing the acoustic spectra measured at two optical wavelengths. Using optical-resolution photoacoustic microscopy, we quantified the absolute optical absorption of black ink samples with various concentrations. We also quantified both the concentration and oxygen saturation of hemoglobin in a live mouse in absolute units.

  6. Bethe-Salpeter calculation of optical-absorption spectra of In2O3 and Ga2O3

    NASA Astrophysics Data System (ADS)

    Varley, Joel B.; Schleife, André

    2015-02-01

    Transparent conducting oxides keep attracting strong scientific interest not only due to their promising potential for ‘transparent electronics’ applications but also due to their intriguing optical absorption characteristics. Materials such as In2O3 and Ga2O3 have complicated unit cells and, consequently, are interesting systems for studying the physics of excitons and anisotropy of optical absorption. Since currently no experimental data is available, for instance, for their dielectric functions across a large photon-energy range, we employ modern first-principles computational approaches based on many-body perturbation theory to provide theoretical-spectroscopy results. Using the Bethe-Salpeter framework, we compute dielectric functions and we compare to spectra computed without excitonic effects. We find that the electron-hole interaction strongly modifies the spectra and we discuss the anisotropy of optical absorption that we find for Ga2O3 in relation to existing theoretical and experimental data.

  7. Fluorescence excitation-emission matrix spectra coupled with parallel factor and regional integration analysis to characterize organic matter humification.

    PubMed

    He, Xiao-Song; Xi, Bei-Dou; Li, Xiang; Pan, Hong-Wei; An, Da; Bai, Shuo-Guo; Li, Dan; Cui, Dong-Yu

    2013-11-01

    The present several humification indexes cannot provide the whole fluorescence information on organic matter composition and the evaluation results from them are inconsistent sometimes. In this study, fluorescence excitation-emission matrix spectra coupled with parallel factor analysis and fluorescence regional integration analysis were utilized to investigate organic matter humification, and the projection pursuit cluster (PPC) model was applied to form a suitable index for overcoming the difficulties in multi-index evaluation. The result showed that the ratio between the volume of humic- and fulvic-like fluorescence region and the volume of protein-like fluorescence region not only revealed the heterogeneity of organic matter, but also provided more accurate information on organic matter humification. In addition, the results showed that the PPC model could be used to characterize integrally the humification, and the projected characteristic value calculated from the PPC model could be used as the integrated humification evaluation index.

  8. Solvatochromic effect in absorption and emission spectra of star-shaped bipolar derivatives of 1,3,5-triazine and carbazole. A time-dependent density functional study.

    PubMed

    Baryshnikov, Gleb V; Bondarchuk, Sergey V; Minaeva, Valentina A; Ågren, Hans; Minaev, Boris F

    2017-02-01

    A series of three star-shaped compounds containing both donor (carbazole) and acceptor (2,4,6-triphenyl-1,3,5-triazine) moieties linked through various linking bridges was studied theoretically at the linear response TD-DFT level of theory to describe their absorption and fluorescence spectra. The concept of a localized charge-transfer excited state has been applied successfully to explain the observed strong solvatochromic effect in the emission spectra of the studied molecules, which can be utilized for the fabrication of color tunable solution-processable OLEDs. The concept is in particularly applicable to donor-acceptor species with a C 3 symmetry point group where the static dipole moment changes dramatically upon electronic excitation. An important peculiarity of the studied molecules is that they are characterized by non-zero values of the HOMO and LUMO orbitals in the same common part of molecular space that provides a large electric dipole transition moment for both light absorption and emission. Graphical abstract Star-shaped C 3 symmetry point group derivatives for color tunable OLEDs.

  9. Do fluorescence and transient absorption probe the same intramolecular charge transfer state of 4-(dimethylamino)benzonitrile?

    SciTech Connect

    Gustavsson, Thomas; Fujiwara, Takashige; Lim, Edward C.

    2009-07-21

    We present here the results of time-resolved absorption and emission experiments for 4-(dimethylamino)benzonitrile in solution, which suggest that the fluorescent intramolecular charge transfer (ICT) state may differ from the twisted ICT (TICT) state observed in transient absorption.

  10. Truncated Newton's optimization scheme for absorption and fluorescence optical tomography: Part I theory and formulation.

    PubMed

    Roy, R; Sevick-Muraca, E

    1999-05-10

    The development of non-invasive, biomedical optical imaging from time-dependent measurements of near-infrared (NIR) light propagation in tissues depends upon two crucial advances: (i) the instrumental tools to enable photon "time-of-flight" measurement within rapid and clinically realistic times, and (ii) the computational tools enabling the reconstruction of interior tissue optical property maps from exterior measurements of photon "time-of-flight" or photon migration. In this contribution, the image reconstruction algorithm is formulated as an optimization problem in which an interior map of tissue optical properties of absorption and fluorescence lifetime is reconstructed from synthetically generated exterior measurements of frequency-domain photon migration (FDPM). The inverse solution is accomplished using a truncated Newtons method with trust region to match synthetic fluorescence FDPM measurements with that predicted by the finite element prediction. The computational overhead and error associated with computing the gradient numerically is minimized upon using modified techniques of reverse automatic differentiation.

  11. Observation of upconversion fluorescence and stimulated emission based on three-photon absorption

    NASA Astrophysics Data System (ADS)

    Yang, Q.; Lin, S.; Xu, L.; Yang, F.; Yang, Y.; Pan, L.; Sun, C.; Li, Y.; Sun, G.; Jiang, Z.

    2005-06-01

    The observations of three-photon-induced frequency-upconversion fluorescence and the highly directional stimulated visible emission in two dyes, 4-[p-(dicyanoethylamino) styryl]-N-methylpyridinium iodide (abbreviated as CEASP) and the complex of CEASP and Ce(NO3) (abbreviated as CEASP-Ce), are reported. The photographs of the forward amplified spontaneous emissions spots, pumped by an optical parametric oscillator idler with a pulse width of 8 ns and a wavelength of 1.3 μ m, are shown. The upconversion fluorescence produced both in dimethyl formamide solution and 2-hydroxyethyl methacrylate (HEMA) polymer spans from green to red, with a cubic dependence on the pump light intensity. The experimental results imply that the existence of the lanthanide ion Ce3 + sensitizes the nonlinear absorption and emission.

  12. Direct Determination of Oxidation States of Uranium in Mixed-Valent Uranium Oxides Using Total Reflection X-ray Fluorescence X-ray Absorption Near-Edge Spectroscopy.

    PubMed

    Sanyal, Kaushik; Khooha, Ajay; Das, Gangadhar; Tiwari, M K; Misra, N L

    2017-01-03

    Total reflection X-ray fluorescence (TXRF)-based X-ray absorption near-edge spectroscopy has been used to determine the oxidation state of uranium in mixed-valent U3O8 and U3O7 uranium oxides. The TXRF spectra of the compounds were measured using variable X-ray energies in the vicinity of the U L3 edge in the TXRF excitation mode at the microfocus beamline of the Indus-2 synchrotron facility. The TXRF-based X-ray absorption near-edge spectroscopy (TXRF-XANES) spectra were deduced from the emission spectra measured using the energies below and above the U L3 edge in the XANES region. The data processing using TXRF-XANES spectra of U(IV), U(V), and U(VI) standard compounds revealed that U present in U3O8 is a mixture of U(V) and U(VI), whereas U in U3O7 is mixture of U(IV) and U(VI). The results obtained in this study are similar to that reported in literature using the U M edge. The present study has demonstrated the possibility of application of TXRF for the oxidation state determination and elemental speciation of radioactive substances in a nondestructive manner with very small amount of sample requirement.

  13. A comparison of the fluorescence spectra of murine and bovine central nervous system (CNS) and other tissues

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Here we describe a comparison of the fluorescence spectra of bovine tissues with murine tissues in order to determine whether spectral features are conserved and whether an appropriate and practical laboratory small animal model system could be identified to be used for investigation of tissue and a...

  14. 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.

  15. Analysis of Atmospheric Trace Constituents from High Resolution Infrared Balloon-Borne and Ground-Based Solar Absorption Spectra

    NASA Technical Reports Server (NTRS)

    Goldman, A.; Murcray, F. J.; Rinsland, C. P.; Blatherwick, R. D.; Murcray, F. H.; Murcray, D. G.

    1991-01-01

    Recent results and ongoing studies of high resolution solar absorption spectra will be presented. The analysis of these spectra is aimed at the identification and quantification of trace constituents important in atmospheric chemistry of the stratosphere and upper troposphere. Analysis of balloon-borne and ground-based spectra obtained at 0.0025/ cm covering the 700-2200/ cm interval will be presented. Results from ground-based 0.02/ cm solar spectra, from several locations such as Denver, South Pole, M. Loa, and New Zealand will also be shown. The 0.0025/ cm spectra show many new spectroscopic features. The analysis of these spectra, along with corresponding laboratory spectra, improves the spectral line parameters, and thus the accuracy of trace constituents quantification. The combination of the recent balloon flights, with earlier flights data since 1978 at 0.02/ cm resolution, provides trends analysis of several stratospheric trace species. Results for COF2, F22, SF6, and other species will be presented. Analysis of several ground-based solar spectra provides trends for HCl, HF and other species. The retrieval methods used for total column density and altitude distribution for both ground-based and balloon-borne spectra will be presented. These are extended for the analysis of the ground-based spectra to be obtained by the high resolution interferometers of the Network for Detection of Stratospheric Change (NDSC). Progress or the University of Denver studies for the NDSC will be presented. This will include intercomparison of solar spectra and trace gases retrievals obtained from simultaneous scans by the high resolution (0.0025/ cm) interferometers of BRUKER and BOMEM.

  16. 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

  17. 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.

  18. Density functional calculations of the vibronic structure of electronic absorption spectra.

    PubMed

    Dierksen, Marc; Grimme, Stefan

    2004-02-22

    Calculations of the vibronic structure in electronic spectra of large organic molecules based on density functional methods are presented. The geometries of the excited states are obtained from time-dependent density functional (TDDFT) calculations employing the B3LYP hybrid functional. The vibrational functions and transition dipole moment derivatives are calculated within the harmonic approximation by finite difference of analytical gradients and the transition dipole moment, respectively. Normal mode mixing is taken into account by the Duschinsky transformation. The vibronic structure of strongly dipole-allowed transitions is calculated within the Franck-Condon approximation. Weakly dipole-allowed and dipole-forbidden transitions are treated within the Franck-Condon-Herzberg-Teller and Herzberg-Teller approximation, respectively. The absorption spectra of several organic pi systems (anthracene, pentacene, pyrene, octatetraene, styrene, azulene, phenoxyl) are calculated and compared with experimental data. For dipole-allowed transitions in general a very good agreement between theory and experiment is obtained. This indicates the good quality of the optimized geometries and harmonic force fields. Larger errors are found for the weakly dipole-allowed S0 --> S1 transition of pyrene which can tentatively be assigned to TDDFT errors for the relative energies of excited states close to the target state. The weak bands of azulene and phenoxyl are very well described within the Franck-Condon approximation which can be explained by the large energy gap (>1.2 eV) to higher-lying excited states leading to small vibronic couplings. Once corrections are made for the errors in the theoretical 0-0 transition energies, the TDDFT approach to calculate vibronic structure seems to outperform both widely used ab initio methods based on configuration interaction singles or complete active space self-consistent field wave functions and semiempirical treatments regarding accuracy

  19. 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

  20. 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.

  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. Multiple pre-edge structures in Cu K -edge x-ray absorption spectra of high- Tc cuprates revealed by high-resolution x-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Gougoussis, C.; Rueff, J.-P.; Calandra, M.; D'Astuto, M.; Jarrige, I.; Ishii, H.; Shukla, A.; Yamada, I.; Azuma, M.; Takano, M.

    2010-06-01

    Using high-resolution x-ray absorption spectroscopy and state-of-the-art electronic structure calculations we demonstrate that the pre-edge region at the Cu K edge of high- Tc cuprates is composed of several excitations invisible in standard x-ray absorption spectra. We consider in detail the case of Ca2-xCuO2Cl2 and show that the many pre-edge excitations (two for c -axis polarization, four for in-plane polarization and out-of-plane incident x-ray momentum) are dominated by off-site transitions and intersite hybridization. This demonstrates the relevance of approaches beyond the single-site model for the description of the pre edges of correlated materials. Finally, we show the occurrence of a doubling of the main edge peak that is most visible when the polarization is along the c axis. This doubling, that has not been seen in any previous absorption data in cuprates, is not reproduced by first-principles calculations. We suggest that this peak is due to many-body charge-transfer excitations while all the other visible far-edge structures are single particle in origin. Our work indicates that previous interpretations of the Cu K -edge x-ray absorption spectra in high- Tc cuprates can be profitably reconsidered.

  3. 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.

  4. Synthesis and evaluation of changes induced by solvent and substituent in electronic absorption spectra of some azo disperse dyes.

    PubMed

    Mohammadi, Asadollah; Yazdanbakhsh, Mohammad Reza; Farahnak, Lahya

    2012-04-01

    Five azo disperse dyes were prepared by diazotizing 4'-aminoacetophenone and p-anisidine and coupling with varies N-alkylated aromatic amines. Characterization of the dyes was carried out by using UV-vis, FTIR and 1H NMR spectroscopic techniques. The electronic absorption spectra of dyes are determined at room temperature in fifteen solvents with different polarities. The solvent dependent maximum absorption band shifts, were investigated using dielectric constant (ɛ), refractive index (n) and Kamlet-Taft polarity parameters (hydrogen bond donating ability (α), hydrogen bond accepting ability (β) and dipolarity/polarizability polarity scale (π*)). Acceptable agreement was found between the maximum absorption band of dyes and solvent polarity parameters especially with π*. The effect of substituents of coupler and/or diazo component on the color of dyes was investigated. The effects of acid and base on the visible absorption maxima of the dyes are also reported.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. Material/element-dependent fluorescence-yield modes on soft X-ray absorption spectroscopy of cathode materials for Li-ion batteries

    DOE PAGES

    Asakura, Daisuke; Hosono, Eiji; Nanba, Yusuke; ...

    2016-03-07

    Here, we evaluate the utilities of fluorescence-yield (FY) modes in soft X-ray absorption spectroscopy (XAS) of several cathodematerials 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 NiL3 edge. The distortions were suppressed for the inverse-partial-FY (IPFY) spectra. We found that, in the cathodematerials, 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 NiL edge whichmore » is far from the O K edge.« less

  10. 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.

  11. Ground state bromine atom density measurements by two-photon absorption laser-induced fluorescence

    NASA Astrophysics Data System (ADS)

    Sirse, N.; Foucher, M.; Chabert, P.; Booth, J.-P.

    2014-12-01

    Ground state bromine atom detection by two-photon absorption laser-induced fluorescence (TALIF) is demonstrated. The (4p5) {^2Po3/2} bromine atoms are excited by two-photon absorption at 252.594 nm to the (5p) {^4So3/2} state and detected by 635.25 nm fluorescence to the (5s) 4P5/2 state. The atoms are generated in a radio-frequency inductively-coupled plasma in pure HBr. The excitation laser also causes some photodissociation of HBr molecules, but this can be minimized by not focussing the laser beam, still giving adequate signal levels. We determined the natural lifetime of the emitting (5p) {^4So3/2} state, τf^Br*=30.9 +/- 1.4 ns and the rate constant for quenching of this state by collision with HBr molecules, k_HBrQ = 1.02 +/- 0.07× 10-15 m3 s-1 .

  12. 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.

  13. Simulating the absorption spectra of helium clusters (N = 70, 150, 231, 300) using a charge transfer correction to superposition of fragment single excitations.

    PubMed

    Ge, Qinghui; Mao, Yuezhi; White, Alec F; Epifanovsky, Evgeny; Closser, Kristina D; Head-Gordon, Martin

    2017-01-28

    Simulations of the n = 2 absorption spectra of HeN (N = 70, 150, 231, 300) clusters are reported, with nuclear configurations sampled by path integral molecular dynamics. The electronic structure is treated by a new approach, ALMO-CIS+CT, which is a formulation of configuration interaction singles (CIS) based on absolutely localized molecular orbitals (ALMOs). The method generalizes the previously reported ALMO-CIS model [K. D. Closser et al. J. Chem. Theory Comput. 11, 5791 (2015)] to include spatially localized charge transfer (CT) effects. It is designed to recover large numbers of excited states in atomic and molecular clusters, such as the entire n = 2 Rydberg band in helium clusters. ALMO-CIS+CT is shown to recover most of the error caused by neglecting charge transfer in ALMO-CIS and has comparable accuracy to standard CIS for helium clusters. For the n = 2 band, CT stabilizes states towards the blue edge by up to 0.5 eV. ALMO-CIS+CT retains the formal cubic scaling of ALMO-CIS with respect to system size. With improvements to the implementation over that originally reported for ALMO-CIS, ALMO-CIS+CT is able to treat helium clusters with hundreds of atoms using modest computing resources. A detailed simulation of the absorption spectra associated with the 2s and 2p bands of helium clusters up to 300 atoms is reported, using path integral molecular dynamics with a spherical boundary condition to generate atomic configurations at 3 K. The main features of experimentally reported fluorescence excitation spectra for helium clusters are reproduced.

  14. Simulating the absorption spectra of helium clusters (N = 70, 150, 231, 300) using a charge transfer correction to superposition of fragment single excitations

    NASA Astrophysics Data System (ADS)

    Ge, Qinghui; Mao, Yuezhi; White, Alec F.; Epifanovsky, Evgeny; Closser, Kristina D.; Head-Gordon, Martin

    2017-01-01

    Simulations of the n = 2 absorption spectra of HeN (N = 70, 150, 231, 300) clusters are reported, with nuclear configurations sampled by path integral molecular dynamics. The electronic structure is treated by a new approach, ALMO-CIS+CT, which is a formulation of configuration interaction singles (CIS) based on absolutely localized molecular orbitals (ALMOs). The method generalizes the previously reported ALMO-CIS model [K. D. Closser et al. J. Chem. Theory Comput. 11, 5791 (2015)] to include spatially localized charge transfer (CT) effects. It is designed to recover large numbers of excited states in atomic and molecular clusters, such as the entire n = 2 Rydberg band in helium clusters. ALMO-CIS+CT is shown to recover most of the error caused by neglecting charge transfer in ALMO-CIS and has comparable accuracy to standard CIS for helium clusters. For the n = 2 band, CT stabilizes states towards the blue edge by up to 0.5 eV. ALMO-CIS+CT retains the formal cubic scaling of ALMO-CIS with respect to system size. With improvements to the implementation over that originally reported for ALMO-CIS, ALMO-CIS+CT is able to treat helium clusters with hundreds of atoms using modest computing resources. A detailed simulation of the absorption spectra associated with the 2s and 2p bands of helium clusters up to 300 atoms is reported, using path integral molecular dynamics with a spherical boundary condition to generate atomic configurations at 3 K. The main features of experimentally reported fluorescence excitation spectra for helium clusters are reproduced.

  15. 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.

  16. Absorption and fluorescence spectroscopic characterization of BLUF domain of AppA from Rhodobacter sphaeroides

    NASA Astrophysics Data System (ADS)

    Zirak, P.; Penzkofer, A.; Schiereis, T.; Hegemann, P.; Jung, A.; Schlichting, I.

    2005-08-01

    The BLUF domain of the transcriptional anti-repressor protein AppA from the non-sulfur anoxyphototrophic purple bacterium Rhodobacter sphaeroides was characterized by absorption and emission spectroscopy. The BLUF domain constructs AppA 148 (consisting of amino-acid residues 1-148) and AppA 126 (amino-acid residues 1-126) are investigated. The cofactor of the investigated domains is found to consist of a mixture of the flavins riboflavin, FMN, and FAD. The dark-adapted domains exist in two different active receptor conformations (receptor states) with different sub-nanosecond fluorescence lifetimes (BLUF r,f and BLUF r,sl) and a small non-interacting conformation (BLUF nc). The active receptor conformations are transformed to putative signalling states (BLUF s,f and BLUF s,sl) of low fluorescence efficiency and picosecond fluorescence lifetime by blue-light excitation (light-adapted domains). In the dark at room temperature both signalling states recover back to the initial receptor states with a time constant of about 17 min. A quantum yield of signalling state formation of about 25% was determined by intensity dependent transmission measurements. A photo-cycle scheme is presented including photo-induced charge transfer complex formation, charge recombination, and protein binding pocket reorganisation.

  17. 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.

  18. Multivariate curve resolution of synchronous fluorescence spectra matrices of fulvic acids obtained as a function of pH.

    PubMed

    Esteves da Silva, Joaquim C G; Tauler, Romá

    2006-11-01

    Synchronous fluorescence spectra (excitation wavelength range between 280 and 510 nm and wavelength interval of 25 nm) of three samples of fulvic acids (FA) were obtained as a function of the pH, in the range from 2.0 to 10.5, and as a function of the FA concentration, in the range from 20 to 180 mg/L. FA were obtained from composted livestock materials (lsFA), composted sewage sludge (csFA), and Laurentian soil (laFA). Three-dimensional spectral matrices were obtained (wavelength, pH, and FA concentration) and multivariate curve resolution (MCR) was used to calculate spectra and fluorescence intensity profiles for the detected components. Cluster analysis of the calculated spectra showed the existence of similar and unique fluorescent properties in the three FA samples. Some of the calculated fluorescence intensity profiles have a shape compatible with acid-base species distribution diagrams, which allowed pKa values to be estimated, namely, a well-defined acid-base equilibrium with pKa 5.7 +/- 0.2 (lsFA), 6.9 +/- 0.4 (csFA), and 5.5 +/- 0.2 (laFA); and other acid-base systems not well defined with pKa at about 3.0 and 8.6. Other spectral variations revealed the existence of inner-filter effects or self-quenching as the concentration of FA increases.

  19. 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.

  20. Electronic structure and optical absorption spectra of CdSe covered with ZnSe and ZnS epilayers

    NASA Astrophysics Data System (ADS)

    Yun, So Jeong; Lee, Geunsik; Kim, Jai Sam; Shin, Seung Koo; Yoon, Young-Gui

    2006-02-01

    Using the first-principles methods we compute the electronic structure and the absorption spectra for a wurtzite CdSe (0001) slab covered with zincblende ZnSe and ZnS epilayers. For each structure we compute the DOS and the imaginary part of the dielectric function. We find that the semiconductor passivation shifts the 'near Fermi-level' states of the bare CdSe slab down to lower energy levels. The migration suggests the decrease of surface effects and energy loss. We observe the substantial reduction of the abnormal peaks in the absorption spectra of the bare CdSe slab, which seems to be a consequence of the DOS migration. This is consistent with the experimental results that a proper passivation enhance the luminescence efficiency. We also study the case that the epilayer surface is terminated with PH 3 and find the PH 3 passivation also reduces the surface state to some extent.

  1. The structure of the absorption spectra of the quasars Q 0420-388 and Q 1101-264

    NASA Astrophysics Data System (ADS)

    Chernomordik, V. V.

    1988-08-01

    The spectra of the quasars Q 0420-388 and Q 1101-264 are studied in the framework of the shock-wave model of the Lyman-alpha forest in the spectra of distant quasars, in which the origin of Lyman-alpha absorption lines is related to absorption zones in the shells of metagalactic shock waves. It is shown that more that 50 percent of the narrow Lyman-alpha abosrption lines are components of doublets, or pairs of nearby lines with the same equivalent widths. This is in good agreement with the predictions of the shock-wave model. The expected H I column density distribution of the Lyman-alpha lines is calculated and is found to be in agreement with the findings of Atwood et al. (1985).

  2. 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.

  3. Using high-resolution laboratory and ground-based solar spectra to assess CH4 absorption coefficient calculations

    NASA Astrophysics Data System (ADS)

    Mendonca, J.; Strong, K.; Sung, K.; Devi, V. M.; Toon, G. C.; Wunch, D.; Franklin, J. E.

    2017-03-01

    A quadratic-speed-dependent Voigt line shape (qSDV) with line mixing (qSDV+LM), together with spectroscopic line parameters from Devi et al. [1,2] for the 2v3 band of CH4, was used to retrieve total columns of CH4 from atmospheric solar absorption spectra. The qSDV line shape (Tran et al., 2013) [3] with line mixing (Lévy et al., 1992) [4] was implemented into the forward model of GFIT (the retrieval algorithm that is at the heart of the GGG software (Wunch et al., 2015) [5]) to calculate CH4 absorption coefficients. High-resolution laboratory spectra of CH4 were used to assess absorption coefficients calculated using a Voigt line shape and spectroscopic parameters from the atm line list (Toon, 2014) [6]. The same laboratory spectra were used to test absorption coefficients calculated using the qSDV+LM line shape with spectroscopic line parameters from Devi et al. [1,2] for the 2v3 band of CH4 and a Voigt line shape for lines that don't belong to the 2v3 band. The spectral line list for lines that don't belong to the 2v3 band is an amalgamation of multiple spectral line lists. We found that for the P, Q, and R branches of the 2v3 band, the qSDV+LM simulated the laboratory spectra better than the Voigt line shape. The qSDV+LM was also used in the spectral fitting of high-resolution solar absorption spectra from four ground-based remote sensing sites and compared to spectra fitted with a Voigt line shape. The average root mean square (RMS) residual for 131,124 solar absorption spectra fitted with absorption coefficients calculated using the qSDV+LM for the 2v3 band of CH4 and the new spectral line list for lines for lines that don't belong to the 2v3 band, was reduced in the P, Q, and R branches by 5%, 13%, and 3%, respectively when compared with spectra fitted using a Voigt line shape and the atm line list. We found that the average total column of CH4 retrieved from these 131,124 spectra, with the qSDV+LM was 1.1±0.3% higher than the retrievals performed using a

  4. In vivo kinetics and spectra of 5-aminolaevulinic acid-induced fluorescence in an amelanotic melanoma of the hamster.

    PubMed Central

    Abels, C.; Heil, P.; Dellian, M.; Kuhnle, G. E.; Baumgartner, R.; Goetz, A. E.

    1994-01-01

    For successful photodynamic diagnosis (PDD) and effective photodynamic therapy (PDT) with the clinically used 'photosensitiser' 5-aminolaevulinic acid (ALA), knowledge of the maximal fluorescence intensity and of the maximal tumour-host tissue fluorescence ratio following systemic or local application is required. Therefore, time course and type of porphyrin accumulation were investigated in neoplastic and surrounding host tissue by measuring the kinetics and spectra of ALA-induced fluorescence in vivo. Experiments were performed in the amelanotic melanoma A-Mel-3 grown in the dorsal skinfold chamber preparation of Syrian golden hamsters. The kinetics of fluorescent porphyrins was quantified up to 24 h after i.v. injection of 100 mg kg-1, 500 mg kg-1 or 1,000 mg kg-1 body weight ALA by intravital fluorescence microscopy and digital image analysis (n = 18). In separate experiments fluorescence spectra were obtained for each dose by a simultaneous optical multichannel analysing device (n = 3). A three-compartment model was developed to simulate fluorescence kinetics in tumours. Maximal fluorescence intensity (per cent of reference standard; mean +/- s.e.) in the tumour arose 150 min post injection (p.i.) (1,000 mg kg-1, 109 +/- 34%; 500 mg kg-1, 148 +/- 36%) and 120 min p.i. (100 mg kg-1, 16 +/- 8%). The fluorescence in the surrounding host tissue was far less and reached its maximum at 240 min (100 mg kg-1, 6 +/- 3%) and 360 min p.i. (500 mg kg-1, 50 +/- 8%) and (1,000 mg kg-1, 6 +/- 19%). Maximal tumour-host tissue ratio (90:1) was encountered at 90 min after injection of 500 mg kg-1. The spectra of tissue fluorescence showed maxima at 637 nm and 704 nm respectively. After 300 min (host tissue) and 360 min (tumour tissue) additional emission bands at 618 nm and 678 nm were detected. These bands indicate the presence of protoporphyrin IX (PPIX) and of another porphyrin species in the tumour not identified yet. Tumour selectivity of ALA-induced PPIX accumulation

  5. 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.

  6. 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.

  7. Ion pairs of indobenzimidazolo cyanines: a structural study based on conductivity, absorption, fluorescence and 1H-NMR

    NASA Astrophysics Data System (ADS)

    Tatikolov, Aleksandr S.; Ishchenko, Aleksandr A.; Ghelli, Stefano; Ponterini, Glauco

    1998-11-01

    Asymmetric benzimidazolo carbo, di- and tricarbocyanines form ion pairs of the solvent-separated and contact types with different counterions in tetrahydrofuran, toluene and toluene-nitrile mixtures. The dissociation constants of the ion pairs in tetrahydrofuran, evaluated from conductivity data, do not depend on the length of the polymethine chain and show only a small decrease with decreasing counterion size. The absorption and fluorescence excitation spectra of the contact ion pairs exhibit a pronounced hypsochromic shift with respect to the solvated ions and the solvent-separated ion pairs. 1H-NMR experiments have provided information about the electronic structures of the ions of both the asymmetric dyes and the corresponding symmetric carbocyanines. They have also revealed different preferred anion locations in the contact ion pairs of the symmetric indocarbocyanine on one hand, and of the benzimidazolo carbocyanine and the asymmetric dyes on the other. This structural difference is suggested to be a cause of the observed opposite effects of ion pairing on the isomerization kinetics of the two groups of dyes.

  8. Simulation of FREE→FREE Absorption Spectra and the Calculation of Interaction Potentials for Alkali-Rare Gas Atom Pairs

    NASA Astrophysics Data System (ADS)

    Hewitt, J. Darby; Spinka, Thomas M.; Readle, Jason. D.; Eden, J. Gary

    2013-06-01

    We have simulated free→free (X^2Σ^+_{1/2}→B^2Σ^+_{1/2}) absorption spectra for alkali-rare gas pairs. By comparing simulation results with experimental data, we have been able to iteratively determine the form for the B^2Σ^+_{1/2} interaction potential for the system for a range in internuclear separation of 1.5-20 Å. Simulation methods will be presented, as will our results pertaining to Cs-Ar.

  9. 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.

  10. Polarized absorption spectra of aromatic radicals in stretched polymer film. 3. Radical ions of acridine and phenazine

    SciTech Connect

    Sekigucki, K.; Hiratsuka, H.; Tanizaki, Y.; Hatano, Y.

    1980-02-21

    Radical anions and cations of acridine and phenazine have been prepared in polymer film by ..gamma..-ray irradiation at 77 K. For the preparation of radical anions the sample was incorporated into polyethylene film by sec-butylamine, while for radical cations poly(vinyl chloride) film and sec-butyl chloride were used. Polarized absorption spectra of these radical ions have been measured in stretched polymer film and analyzed qualitatively in terms of molecular orbital calculations.

  11. Interacting He and Ar atoms: Revised theoretical interaction potential, dipole moment, and collision-induced absorption spectra.

    PubMed

    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 D7 is obtained by perturbation methods. Collision-induced absorption spectra are computed quantum mechanically and compared with existing measurements.

  12. Calculation of Vibrational and Electronic Excited-State Absorption Spectra of Arsenic-Water Complexes Using Density Functional Theory

    DTIC Science & Technology

    2016-06-03

    of Arsenic- Water Complexes Using Density Functional Theory June 3, 2016 Approved for public release; distribution is unlimited. L. Huang S.g...NUMBER OF PAGES 17. LIMITATION OF ABSTRACT Calculation of Vibrational and Electronic Excited-State Absorption Spectra of Arsenic- Water Complexes Using... water molecules should be associated with response features that are intermediate between that of isolated molecules and that of a bulk system. DFT and

  13. 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.

  14. 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.

  15. Electronic spectra of 2- and 3-tolunitrile in the gas phase. II. Geometry changes from Franck-Condon fits of fluorescence emission spectra.

    PubMed

    Gmerek, Felix; Stuhlmann, Benjamin; Álvarez-Valtierra, Leonardo; Pratt, David W; Schmitt, Michael

    2016-02-28

    We determined the changes of the geometries of 2- and 3-tolunitrile upon excitation to the lowest excited singlet states from Franck-Condon fits of the vibronic intensities in several fluorescence emission spectra and of the rotational constant changes upon excitation. These structural changes can be connected to the altered electron distribution in the molecules and are compared to the results of ab initio calculations. We show how the torsional barriers of the methyl groups in both components are used as probe of the molecular changes upon electronic excitation.

  16. Electronic spectra of 2- and 3-tolunitrile in the gas phase. II. Geometry changes from Franck-Condon fits of fluorescence emission spectra

    NASA Astrophysics Data System (ADS)

    Gmerek, Felix; Stuhlmann, Benjamin; Álvarez-Valtierra, Leonardo; Pratt, David W.; Schmitt, Michael

    2016-02-01

    We determined the changes of the geometries of 2- and 3-tolunitrile upon excitation to the lowest excited singlet states from Franck-Condon fits of the vibronic intensities in several fluorescence emission spectra and of the rotational constant changes upon excitation. These structural changes can be connected to the altered electron distribution in the molecules and are compared to the results of ab initio calculations. We show how the torsional barriers of the methyl groups in both components are used as probe of the molecular changes upon electronic excitation.

  17. Iron speciation in human cancer cells by K-edge total reflection X-ray fluorescence-X-ray absorption near edge structure analysis

    NASA Astrophysics Data System (ADS)

    Polgári, Zs.; Meirer, F.; Sasamori, S.; Ingerle, D.; Pepponi, G.; Streli, C.; Rickers, K.; Réti, A.; Budai, B.; Szoboszlai, N.; Záray, G.

    2011-03-01

    X-ray absorption near edge structure (XANES) analysis in combination with synchrotron radiation induced total reflection X-ray fluorescence (SR-TXRF) acquisition was used to determine the oxidation state of Fe in human cancer cells and simultaneously their elemental composition by applying a simple sample preparation procedure consisting of pipetting the cell suspension onto the quartz reflectors. XANES spectra of several inorganic and organic iron compounds were recorded and compared to that of different cell lines. The XANES spectra of cells, independently from the phase of cell growth and cell type were very similar to that of ferritin, the main Fe store within the cell. The spectra obtained after CoCl 2 or NiCl 2 treatment, which could mimic a hypoxic state of cells, did not differ noticeably from that of the ferritin standard. After 5-fluorouracil administration, which could also induce an oxidative-stress in cells, the absorption edge position was shifted toward higher energies representing a higher oxidation state of Fe. Intense treatment with antimycin A, which inhibits electron transfer in the respiratory chain, resulted in minor changes in the spectrum, resembling rather the N-donor Fe-α,α'-dipyridyl complex at the oxidation energy of Fe(III), than ferritin. The incorporation of Co and Ni in the cells was followed by SR-TXRF measurements.

  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. Förster resonance energy transfer, absorption and emission spectra in multichromophoric systems. III. Exact stochastic path integral evaluation.

    PubMed

    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.

  20. Electric field effect on the nonlinear and linear intersubband absorption spectra in CdTe/ZnTe spherical quantum dot

    NASA Astrophysics Data System (ADS)

    Kostić, Radmila; Stojanović, Dušanka

    2012-01-01

    Linear and nonlinear absorption spectra of neutral (D0) hydrogenic impurity located at the center of the CdTe/ZnTe spherical quantum dot (QD) were investigated after assuming a spherically symmetric confining potential of finite depth. Calculations were performed under the effective mass approximation on the basis of exact solution of the Schrödinger and Poisson equations. Eigenfunctions were expressed in terms of the Whittaker and Coulomb wave functions. Results for D0 impurity energies of ground 1s, and excited 2p, 3d, and 2s states strongly depend on QD radius if it does not exceed a few effective Bohr radius. Wave functions and Stark shift energy levels in external electric field were determined from a variational-calculus approach for states labeled m=0. The absorption spectra for intersubband transitions were found to depend strongly on the QD radius. Whether or not the impurity is present, the peak energy of absorption decreases with increasing QD radius. An external electric field increases the transition energy but does not significantly change absorption characteristics.

  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. pH-dependent absorption spectra of rhodopsin mutant E113Q: On the role of counterions and protein

    NASA Astrophysics Data System (ADS)

    Xie, Peng; Zhou, Panwang; Alsaedi, Ahmed; Zhang, Yan

    2017-03-01

    The absorption spectra of bovine rhodopsin mutant E113Q in solutions were investigated at the molecular level by using a hybrid quantum mechanics/molecular mechanics (QM/MM) method. The calculations suggest the mechanism of the absorption variations of E113Q at different pH values. The results indicate that the polarizations of the counterions in the vicinity of Schiff base under protonation and unprotonation states of the mutant E113Q would be a crucial factor to change the energy gap of the retinal to tune the absorption spectra. Glu-181 residue, which is close to the chromophore, cannot serve as the counterion of the protonated Schiff base of E113Q in dark state. Moreover, the results of the absorption maximum in mutant E113Q with the various anions (Cl-, Br-, I- and NO3-) manifested that the mutant E113Q could have the potential for use as a template of anion biosensors at visible wavelength.

  3. 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

  4. Absorption, fluorescence, and acid-base equilibria of rhodamines in micellar media of sodium dodecyl sulfate

    NASA Astrophysics Data System (ADS)

    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 pKaapp = 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.

  5. 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

  6. Advanced glycation end products in hemodialysates as fluorescent and optical absorption markers of patients mortality

    NASA Astrophysics Data System (ADS)

    Kuznetsov, A.; Frorip, A.; Maiste, A.; Ots-Rosenberg, M.; Sünter, A.; Sablonin, J.; Vasil'chenko, J.

    2014-10-01

    Hemodialysate (HD) samples collected from the end stage renal disease patients (ESRD Pts) were used for search for possible correlation between the intensity of HD visible auto-fluorescence (VF) detected at 420 nm as well as their optical absorption at 320 nm and the mortality events among the Pts. Previous but strongly promising correlations has been found in both cases which deserve further supplementation and examination. Investigation of possible influence of quenchers onto the VF intensity has been carried out. Endogenous inorganic ions present in biological fluids (serum, urine and HD) (Na, K, Ca, Mg and ammonia) do not affect the VF intensity remarkably but exogenous Al ions do that indirectly and specifically. Carbon based entities (nanoparticles of graphene type, humins) quench the VF effectively according to the Stern-Volmer law. The quenching phenomena and influence of aluminium must be taken into account by the further investigations, medical care and nutrition.

  7. Invited review article: Imaging techniques for harmonic and multiphoton absorption fluorescence microscopy.

    PubMed

    Carriles, Ramón; Schafer, Dawn N; Sheetz, Kraig E; Field, Jeffrey J; Cisek, Richard; Barzda, Virginijus; Sylvester, Anne W; Squier, Jeffrey A

    2009-08-01

    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.

  8. Computed and Experimental Absorption Spectra of the Perovskite CH3NH3PbI3.

    PubMed

    Zhu, Xi; Su, Haibin; Marcus, Rudolph A; Michel-Beyerle, Maria E

    2014-09-04

    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.

  9. 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.

  10. 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.

  11. Heavy Metals Effect on Cyanobacteria Synechocystis aquatilis Study Using Absorption, Fluorescence, Flow Cytometry, and Photothermal Measurements

    NASA Astrophysics Data System (ADS)

    Dudkowiak, A.; Olejarz, B.; Łukasiewicz, J.; Banaszek, J.; Sikora, J.; Wiktorowicz, K.

    2011-04-01

    The toxic effect of six heavy metals on cyanobacteria Synechocystis aquatilis was studied by absorption, fluorescence, flow cytometry, and photothermal measurements. This study indicates that at the concentration used, the cyanobacteria are more sensitive to silver, copper, and mercury than to cadmium, lead, and zinc metals. Disregarding the decrease in the yields of the related radiative processes caused by photochemical processes and/or damage to phycobilisomes, no changes were detected in the efficiency of thermal deactivation processes within a few microseconds, which can indicate the lack of disturbances in the photosynthetic light reaction and the lack of damage to the photosystem caused by the heavy metal ions in the concentrations used. The results demonstrate that the relative values of fluorescence yield as well as promptly generated heat calculated for the metal-affected and unaffected (reference) bacteria are sensitive indicators of environmental pollution with heavy metal ions, whereas the complementary methods proposed could be used as a noninvasive and fast procedure for in vivo assessment of their toxicity.

  12. 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

  13. Franck-Condon analysis of the S0 --> T1 absorption and phosphorescence spectra of biphenyl and bridged derivatives

    NASA Astrophysics Data System (ADS)

    Negri, Fabrizia; Zgierski, Marek Z.

    1992-11-01

    The equilibrium geometry and the vibrational force field of the ground and the lowest triplet electronic states of biphenyl and three bridged derivatives-biphenylene, fluorene and phenanthrene-are computed by using an updated version of the QCFF/PI (Quantum Chemical Force Field/π electron) Hamiltonian. The displacement parameters between T1 and S0 are obtained and used to model the S0→T1 absorption and the phosphorescence spectra. The calculated Franck-Condon envelopes are found to be in excellent agreement with the vibrational structure of the observed spectra. The common features of the phosphorescence spectra of biphenyl and fluorene are related to the same orbital nature of the lowest triplet state. The observed asymmetry between the phosphorescence and singlet-triplet absorption spectra of biphenyl is reproduced when the twisted equilibrium geometry of S0 is considered. It is shown that evidence of the nonplanarity of the ground state of biphenyl is manifested by the lower intensity of the band observed in the phosphorescence at 747 cm-1 with respect to the intensity of the same band in fluorene. The increased vibrational activity calculated in the lower frequency region for biphenylene and phenanthrene agrees with the observed spectra and reflects the different orbital nature of the lowest triplet state of the two strongly perturbed bridged derivatives with respect to biphenyl and fluorene. From the analysis of the computed vibrational frequencies, it is suggested that the false origin of the symmetry forbidden phosphorescence of biphenylene is due to the lowest out-of-plane mode of au symmetry.

  14. 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.

  15. 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.

  16. 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

  17. Photonic reagents for concentration measurement of flu-orescent proteins with overlapping spectra.

    PubMed

    Goun, Alexei; Bondar, Denys I; Er, Ali O; Quine, Zachary; Rabitz, Herschel A

    2016-05-16

    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.

  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. High resolution infrared absorption spectra of various trace gases present in the upper atmosphere of the Earth

    NASA Technical Reports Server (NTRS)

    Hunt, Robert H.

    1988-01-01

    The objective of NASA Grant NsG 7473 was to obtain and analyze high resolution infrared absorption spectra of various trace gases present in the Earth's upper atmosphere. The goal of the spectral analysis was to obtain values of absorption line strengths, widths and frequencies of sufficient accuracy for use in upper atmosphere trace gas monitoring. During the early phase of the grant, high resolution spectra were obtained from two instruments. One was the 0.02/cm resolution vacuum grating spectrometer at the Florida State University and the other was the 0.01/cm resolution Fourier transform spectrometer at the McMath solar telescope at the Kitt Peak Observatory. Using these instruments, a considerable amount of spectra of methane and hydrogen peroxide were obtained and analyzed. During the latter years of the project, data taking was halted while efforts were devoted to building a new 0.0025/cm resolution vacuum Fourier transform spectrometer. Progress during this phase of the grant then became greatly slowed due to a lack of suitable graduate students in the program. However, the instrument was completed and brought to the point of producing interferograms.

  20. 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.

  1. 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).

  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. Synchrotron Polarization and Synchrotron Self-absorption Spectra for a Power-law Particle Distribution with Finite Energy Range

    NASA Astrophysics Data System (ADS)

    Fouka, M.; Ouichaoui, S.

    2011-12-01

    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(γ) ~ γ-p with γ1 < γ < γ2, especially for a finite high-energy limit, γ2, in the case of an arbitrary pitch angle. The new results inferred concern more especially the high-frequency range x Gt η2 with parameter η = γ2/γ1. 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, αν, for the high-frequency range ν Gt ν2 (with ν2 the synchrotron frequency corresponding to γ2). 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.

  4. Vibrational absorption spectra from vibrational coupled cluster damped linear response functions calculated using an asymmetric Lanczos algorithm

    NASA Astrophysics Data System (ADS)

    Thomsen, Bo; Hansen, Mikkel Bo; Seidler, Peter; Christiansen, Ove

    2012-03-01

    We report the theory and implementation of vibrational coupled cluster (VCC) damped response functions. From the imaginary part of the damped VCC response function the absorption as function of frequency can be obtained, requiring formally the solution of the now complex VCC response equations. The absorption spectrum can in this formulation be seen as a matrix function of the characteristic VCC Jacobian response matrix. The asymmetric matrix version of the Lanczos method is used to generate a tridiagonal representation of the VCC response Jacobian. Solving the complex response equations in the relevant Lanczos space provides a method for calculating the VCC damped response functions and thereby subsequently the absorption spectra. The convergence behaviour of the algorithm is discussed theoretically and tested for different levels of completeness of the VCC expansion. Comparison is made with results from the recently reported [P. Seidler, M. B. Hansen, W. Györffy, D. Toffoli, and O. Christiansen, J. Chem. Phys. 132, 164105 (2010)] vibrational configuration interaction damped response function calculated using a symmetric Lanczos algorithm. Calculations of IR spectra of oxazole, cyclopropene, and uracil illustrate the usefulness of the new VCC based method.

  5. Vibrational absorption spectra from vibrational coupled cluster damped linear response functions calculated using an asymmetric Lanczos algorithm.

    PubMed

    Thomsen, Bo; Hansen, Mikkel Bo; Seidler, Peter; Christiansen, Ove

    2012-03-28

    We report the theory and implementation of vibrational coupled cluster (VCC) damped response functions. From the imaginary part of the damped VCC response function the absorption as function of frequency can be obtained, requiring formally the solution of the now complex VCC response equations. The absorption spectrum can in this formulation be seen as a matrix function of the characteristic VCC Jacobian response matrix. The asymmetric matrix version of the Lanczos method is used to generate a tridiagonal representation of the VCC response Jacobian. Solving the complex response equations in the relevant Lanczos space provides a method for calculating the VCC damped response functions and thereby subsequently the absorption spectra. The convergence behaviour of the algorithm is discussed theoretically and tested for different levels of completeness of the VCC expansion. Comparison is made with results from the recently reported [P. Seidler, M. B. Hansen, W. Györffy, D. Toffoli, and O. Christiansen, J. Chem. Phys. 132, 164105 (2010)] vibrational configuration interaction damped response function calculated using a symmetric Lanczos algorithm. Calculations of IR spectra of oxazole, cyclopropene, and uracil illustrate the usefulness of the new VCC based method.

  6. 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.

  7. Excited-state intramolecular proton transfer in 3-hyroxyflavone isolated in solid argon: fluorescence and fluorescence-excitation spectra and tautomer fluorescence rise time

    SciTech Connect

    Dick, B.; Ernsting, N.P.

    1987-07-30

    The fluorescence properties of 3-hydroxyflavone isolated in solid argon at 15 K have been investigated. Upon electronic excitation the molecules undergo rapid intramolecular proton transfer. No fluorescence from the excited state of the normal form of the molecule could be detected. Perturbations due to hydrogen-bonding impurities which produce serious experimental problems in hydrocarbon glasses are largely suppressed in argon matrices. The rise of the green fluorescence of the tautomer was studied with excitation pulses of 230-fs duration and streak camera detection. An apparent tautomer fluorescence rise time of 2.7 ps was obtained by deconvolution. A comparative measurement of the dye coumarine 6 yielded an apparent fluorescence rise time of 2.5 ps, which can be entirely attributed to the group velocity dispersion of the streak camera optics. This indicates a rate constant for excited-state intramolecular proton transfer in 3-hydroxyflavone of greater than 10/sup 12/ s/sup -1/.

  8. 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.

  9. Studying the complex absorption profiles of Si IV in 21 HiBALQSO spectra

    NASA Astrophysics Data System (ADS)

    Stathopoulos, D.; Danezis, E.; Lyratzi, E.; Antoniou, A.; Popović, L. Č.; Tzimeas, D.; Dimitrijević, M. S.

    2014-12-01

    We investigate the physical conditions and kinematics of broad absorption line region clouds of Si IV in 21 HiBAL Quasars. We use the Danezis et al. method [1], [2], [3] in order to fit and analyze the broad absorption troughs of Si IV resonance lines in the UV region of the electromagnetic spectrum. We find that the BAL flow is not smooth but instead plasma clouds are formed in it. BAL troughs present multicomponent structure which indicates the existence of more than one absorbing cloud in the line of sight, where every absorbing cloud produces a Si IV doublet. We show that the blending of these doublets produces the apparent broad absorption troughs we observe. One of our main achievements is that we managed to decompose and deblend each complex absorption trough to the individual doublets that it consists of. Apart from that, we succeeded in deblending the resonance lines of every doublet. By achieving accurate fits to the BAL troughs we calculated some physical and kinematical parameters that describe the plasma clouds in the line of sight. These parameters are: the radial outflow velocities of the clouds, the random velocities of ions inside each plasma cloud, the apparent optical depth in the center of every absorption component, the FWHM and the equivalent width. As a final step we correlate these physical parameters in order to draw useful conclusions.

  10. Short-Range Characterization of the MeAr (Me=Zn, Cd) Ground-State Potentials from Fluorescence Spectra

    NASA Astrophysics Data System (ADS)

    Koperski, J.; Czajkowski, M.

    2002-04-01

    First-time observed D1(1Π)v‧=10→X0+(1Σ) fluorescence in ZnAr, and A0+(3Π)v‧=4→X0+ and D1(1Π)v‧=7,8→X0+ fluorescence in CdAr van der Waals (vdW) molecules were produced in a continuous supersonic molecular beam crossed with a pulsed dye-laser beam, following excitation of single vibronic levels. The dispersed fluorescence spectra displayed characteristic Condon internal diffraction (CID) patterns consisting of bound-free, reflection type, continuous spectra, and, in certain cases, bound-bound discrete features. An analysis of the A0+→X0+ and D1→X0+ bound-bound spectra indicates that Morse functions are adequate representations of the X0+ potential energy (PE) curves below their dissociation limits. In simulation of the A0+→X0+ and D1→X0+ bound-free spectra, the Morse, Lennard-Jones L-J(n-6), and Maitland-Smith M-S(n0,n1) functions were tested, and the respective M-S(11.3, 9.0) and M-S(10.6, 7.0) potentials were found to be good representations for the repulsive walls of the X0+ PE curves of ZnAr and CdAr, respectively, over the short range, R=2.45-4.38 Å (ZnAr) and R=2.85-4.31 Å (CdAr), of internuclear separations.

  11. The UV absorption of nucleobases: semi-classical ab initio spectra simulations.

    PubMed

    Barbatti, Mario; Aquino, Adelia J A; Lischka, Hans

    2010-05-21

    Semi-classical simulations of the UV-photoabsorption cross sections of adenine, guanine, cytosine, thymine, and uracil in gas phase were performed at the resolution-of-identity coupled cluster to the second-order (RI-CC2) level. With the exception of cytosine, the spectra of the other four nucleobases show a two band pattern separated by a low intensity region. The spectrum of cytosine is shaped by a sequence of three bands of increasing intensity. The first band of guanine is composed by two pipi* transitions of similar intensities. The analysis of individual contributions to the spectra allows a detailed assignment of bands. It is shown that the semi-classical simulations are able to predict general features of the experimental spectra, including their absolute intensities.

  12. Optical absorption spectra and structures of Ag{6/+} and Ag{8/+}

    NASA Astrophysics Data System (ADS)

    Shayeghi, A.; Götz, D. A.; Johnston, R. L.; Schäfer, R.

    2015-06-01

    This work presents optical photodissociation spectra of the Ag{6/+} and the Ag{8/+} clusters in the photon energy range ħω = 1.9-4.4 eV. Experimental spectra are interpreted by means of range separated TDDFT using the LC- ωPBEh and HSE06 functionals, where putative global minimum structures are obtained by the new pool-based Birmingham Cluster Genetic Algorithm, coupled with density functional theory. Structural assignment is facilitated by additionally taking data from previous ion mobility experiments into account. Both functionals reproduce the measured spectra very well, whereas HSE06 shows an almost quantitative agreement, questioning the importance of Hartree-Fock exchange in the long-range part of the range separated functional.

  13. Direct determination of cadmium speciation in municipal solid waste fly ashes by synchrotron radiation induced mu-X-ray fluorescence and mu-X-ray absorption spectroscopy.

    PubMed

    Pinzani, Maria Caterina Camerani; Somogyi, Andrea; Simionovici, Alexandre S; Ansell, Stuart; Steenari, Britt-Marie; Lindqvist, Oliver

    2002-07-15

    Cadmium is a toxic metal that causes environmental concern in connection with utilization and land filling of ash from combustion of municipal solid waste (MSW). Collecting information about the chemical associations of Cd in ash is fundamental since this affects its solubility and leachability from the ash material. In the work presented here, the content, distribution, and chemical forms of toxic metals especially of Cd on/in individual Municipal Solid Waste (MSW) fly ash particles have been investigated in situ by synchrotron radiation induced mu-X-ray fluorescence and absorption spectrometry. The use of an excitation energy of 27 keV made it possible to detect trace metals, such as Cd, present at ppm levels routinely. Changing the excitation energy in the vicinity of the absorption edge of Cd (26.71 keV), the absorption spectra of this element were measured for the first time in this high energy range in micron-sized spots of individual fly ash particles. The measurements indicated Cd to be preferably concentrated in some small areas ("hot-spots") with high concentration (up to 200 ppm) rather than in a homogeneous distribution or as a thin coating on the whole particle surface, making the surface-reaction the most probable mechanism of Cd enrichment during MSW combustion processes. Comparisons of XAS spectra of fly ashes and reference compounds showed that in the particles studied Cd is present in the oxidation state +2. Analyses of linear combinations of standard spectra allowed estimating the Cd presence within fly ash particles as an admixture of primarily CdSO4, CdO, and CdCl2 as well as an unidentified compound not included as a standard.

  14. 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.

  15. On the time-dependent calculation of angular averaged vibronic absorption spectra with an application to molecular aggregates

    NASA Astrophysics Data System (ADS)

    Brüning, Christoph; Engel, Volker

    2017-01-01

    We introduce an efficient method to determine angular averaged absorption spectra for cases where electronic transitions take place to a manifold of N coupled excited states. The approach rests on the calculation of time-dependent auto-correlation functions which, upon Fourier-transform yield the spectrum. Assuming the Condon-approximation, it is shown that three wave-packet propagations are sufficient to calculate the spectrum. This is in contrast to a direct approach where it is necessary to perform N propagations to arrive at N2 cross-correlation functions. The reduction in computation time is of importance for larger molecular aggregates where the number N is determined by the aggregate size. We provide an example by determining spectra for macrocyclic dyes in different dipole-geometries.

  16. 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.

  17. 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.

  18. The effect of absorption and coherent interference in the photoluminescence and electroluminescence spectra of SRO/SRN MIS capacitors.

    PubMed

    Juvert, Joan; González-Fernández, Alfredo Abelardo; Llobera, Andreu; Domínguez, Carlos

    2013-04-22

    In this paper we present a technique that can be used to study the effect of absorption and coherent interference in the luminescence of multilayer structures. We apply the technique to the measured photoluminescence and electroluminescence spectra of MIS capacitors where the insulator is composed of a silicon rich oxide (SRO)/silicon rich nitride (SRN) bilayer structure. We remove the effect of the multilayer stack on the measured photoluminescence spectrum of the samples without the metal contact to find the intrinsic spectrum. Then we apply the effect of the MIS structure on the intrinsic spectrum in order to calculate the electroluminescence spectrum. Good agreement with the experimentally measured EL spectrum is found. We discuss which parameters affect the spectra most significantly.

  19. Cooperative enhancement of TPA in cruciform double-chain DSB derivation: a femtosecond transient absorption spectra study

    NASA Astrophysics Data System (ADS)

    He, X.; Wang, Y.; Yang, Z.; Ma, Y.; Yang, Y.

    2010-09-01

    Femtosecond time-resolved transient absorption (TA) spectra study was adopted to study the mechanism of the cooperative enhancement of two-photon absorption (TPA) cross section from the linear structure 1,4-di(4'-N,N-diphenylaminostyryl)benzene (DPA-DSB) to its cruciform double-chain dimer DPA-TSB. The results suggested that a non-emissive intramolecular charge-transfer (ICT) state, ICT’, was present upon excitation in the dimer, which was absent in the monomer. The existence of this non-emissive state, indicating the enhancement of the intramolecular charge-transfer of the dimer, should be the reason for the cooperative enhancement of the TPA cross section of the dimer compared to the monomer.

  20. 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.