Sample records for absorption spectra fluorescence

  1. 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).

  2. 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.

  3. Studies of Time-Resolved Fluorescence Spectroscopy and Resolved Absorption Spectra of Nucleic Acid Components.

    NASA Astrophysics Data System (ADS)

    Fu, Yingxian

    1993-01-01

    There is considerable uncertainty about dynamic aspects of the photophysics of the adenylyl chromophore, stemming from the discordant values reported for the room temperature fluorescence lifetimes (tau_1 = 5 ps, tau_2 = 330 ps for 9MeAde; tau_1 = 290 ps, tau_2 = 4.17 ns for ATP). Spectra reported in conjunction with these lifetimes create difficulties in assignment of emission. To clarify this situation I have investigated the fluorescence decay times and time -resolved emission spectra of adenylyl compounds under a variety of conditions (concentration, pH, solvent) using sub-ns laser excitation at 265 nm together with gated fast sampling (100 ps) detection and signal averaging. Multi -component decays and spectra are observed in aqueous solution. Major slow components (tau = 4.4 +/- 0.2 ns) with emission maxima at 380 nm are found for all components at pH 1.1 and for ATP at pH 4.4. At pH 7 a fast component (<100 ps) predominates. There is no marked evidence for a concentration dependence, the oscillator strengths are 10^ {-3}-10^{-5} and transitions must be classified as weakly forbidden. Single component emission is observed in acetonitrile and ethanol. The UV absorption spectra of biomolecules d(CG) and polyd(GC)cdotpolyd(GC) exhibit the different hypochromic effects due to different interactions between guanosine(G) and cytidine(C) in stacked form. The present work has been carried out to explain this quantitatively. To approach this problem the absorption spectra of G and C have been resolved into gaussian components using the PeakFit program. The absorption spectra (220-310 nm) of d(CG) and polyd(GC)cdotpolyd(GC) have been fitted with gaussian components of G and C (in the order of increasing energy, G1 and G2, and C1, C2 and C3, respectively), and the contribution to both spectra from individual gaussians is estimated in terms of oscillator strengths. The fitting results suggest that the small hypochromism in absorption spectrum of d(CG) may be attributed

  4. The absorption, fluorescence and phosphorescence spectra of α and β-F, Cl, Br-naphthalenes in crystalline matrixes at 77 K

    NASA Astrophysics Data System (ADS)

    Iliescu, T.; Milea, I.; Abdolrahman, P. M.

    1984-03-01

    The paper studies the absorption, fluorescence and phosphorescence spectra of α and β-F, Cl, Br-naphtalenes (α, β-F, Cl,BrN) in different matrixes at 77 K and different concentrations. From these spectra one obtaines the vibrational frequences.

  5. Absorption and fluorescence spectra of heterocyclic isomers from long-range-corrected density functional theory in polarizable continuum approach.

    PubMed

    Kityk, Andriy V

    2012-03-22

    Long-range-corrected (LC) DFT/TDDFT methods may provide adequate description of ground and excited state properties; however, accuracy of such an approach depends much on a range separation (exchange screening) representing adjustable model parameter. Its relation to a size or specific of molecular systems has been explored in numerous studies, whereas the effect of solvent environment is usually ignored during the evaluation of state properties. To benchmark and assess the quality of the LC-DFT/TDDFT formalism, we report the optical absorption and fluorescence emission energies of organic heterocyclic isomers, DPIPQ and PTNA, calculated by LC-BLYP DFT/TDDFT method in the polarizable continuum (PCM) approach. The calculations are compared with the optical absorption and fluorescence spectra measured in organic solvents of different polarity. Despite a considerable structural difference, both dyes exhibit quite similar range separations being somewhat different for the optical absorption and fluorescence emission processes. Properly parametrized LC-BLYP xc-potential well reproduces basic features of the optical absorption spectra including the electronic transitions to higher excited states. The DFT/TDDFT/PCM analysis correctly predicts the solvation trends although solvatochromic shifts of the electronic transition energies appear to be evidently underestimated in most cases, especially for the fluorescence emission. Considering the discrepancy between the experiment and theory, evaluated state dipole moments and solvation corrections to the exchange screening are analyzed. The results of the present study emphasize the importance of a solvent-dependent range separation in DFT/TDDFT/PCM calculations for investigating excited state properties. © 2012 American Chemical Society

  6. Measurement of two-photon-absorption spectra through nonlinear fluorescence produced by a line-shaped excitation beam.

    PubMed

    Hasani, E; Parravicini, J; Tartara, L; Tomaselli, A; Tomassini, D

    2018-05-01

    We propose an innovative experimental approach to estimate the two-photon absorption (TPA) spectrum of a fluorescent material. Our method develops the standard indirect fluorescence-based method for the TPA measurement by employing a line-shaped excitation beam, generating a line-shaped fluorescence emission. Such a configuration, which requires a relatively high amount of optical power, permits to have a greatly increased fluorescence signal, thus avoiding the photon counterdetection devices usually used in these measurements, and allowing to employ detectors such as charge-coupled device (CCD) cameras. The method is finally tested on a fluorescent isothiocyanate sample, whose TPA spectrum, which is measured with the proposed technique, is compared with the TPA spectra reported in the literature, confirming the validity of our experimental approach. © 2018 The Authors Journal of Microscopy © 2018 Royal Microscopical Society.

  7. 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).

  8. Decomposition of the fluorescence spectra of two FAD molecules in electron-transferring flavoprotein from Megasphaera elsdenii.

    PubMed

    Sato, Kyosuke; Nishina, Yasuzo; Shiga, Kiyoshi

    2013-07-01

    Electron-transferring flavoprotein (ETF) from Megasphaera elsdenii contains two FAD molecules, FAD-1 and FAD-2. FAD-2 shows an unusual absorption spectrum with a 400-nm peak. In contrast, ETFs from other sources such as pig contain one FAD and one AMP with the FAD showing a typical flavin absorption spectrum with 380- and 440-nm peaks. It is presumed that FAD-2 is the counterpart of the FAD in other ETFs. In this study, the FAD-1 and FAD-2 fluorescence spectra were determined by titration of FAD-1-bound ETF with FAD using excitation-emission matrix (EEM) fluorescence spectroscopy. The EEM data were globally analysed, and the FAD fluorescence spectra were calculated from the principal components using their respective absorption spectra. The FAD-2 fluorescence spectrum was different from that of pig ETF, which is more intense and blue-shifted. AMP-free pig ETF in acidic solution, which has a comparable absorption spectrum to FAD-2, also had a similar fluorescence spectrum. This result suggests that FAD-2 in M. elsdenii ETF and the FAD in acidic AMP-free pig ETF share a common microenvironment. A review of published ETF fluorescence spectra led to the speculation that the majority of ETF molecules in solution are in the conformation depicted by the crystal structure.

  9. One- and two-photon absorption spectra of the yellow fluorescent protein citrine: effects of intramolecular electron-vibrational coupling and intermolecular interactions

    NASA Astrophysics Data System (ADS)

    Chen, Fasheng; Zhao, Xinyi; Liang, WanZhen

    2018-04-01

    Both the vibrationally resolved and statistically averaged one-photon absorption (OPA) and two-photon absorption (TPA) spectra of the anionic form of chromophore (AC) in its micro-environment of yellow fluorescent protein (YFP) Citrine have been calculated. The result comparison has been made with those of the AC model compounds in vacuo and methanol solution, which allows us to allocate the individual contribution of the intramolecular electron-vibrational coupling, the electrostatic π-stacking interaction between Tyr203 and AC, and the interaction between AC and its micro-environment to the spectra. The results reveal that the non-Condon vibronic coupling effect is responsible for the blue shift of TPA absorption maximum compared with its OPA counterpart corresponding to S0 → S1, and that the π-stacking interaction between Tyr203 and AC alters the relative intensities of TPA maxima, which further enhances the higher-energy vibronic peaks and weakens the lowest-energy peak. The statically averaged OPA and TPA spectra calculated by quantum mechanics/molecular mechanics (QM/MM) methods based on Born-Oppenheimer molecular dynamics simulation largely deviate the experimental spectral lineshapes, which further verifies the significant contribution of non-Condon vibronic coupling effect on the spectra. The interaction of individual amino acid residue or water close to AC+Tyr203 has different effects on the spectra, which may increase/decrease the excitation energy depending on its position and electronic property.

  10. 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

  11. Absorption and emission spectra of Li atoms trapped in rare gas matrices

    NASA Astrophysics Data System (ADS)

    Wright, J. J.; Balling, L. C.

    1980-10-01

    Pulsed-dye-laser excitation has been used to investigate the optical absorption and emission spectra of Li atoms trapped in Ar, Kr, and Xe matrices at 10 °K. Attempts to stabilize Li atoms in a Ne matrix at 2 °K were unsuccessful. Results for all three rare gases were qualitatively the same. White light absorption scans showed a single absorption with three peaks centered near the free-atom 2s→2p transition wavelength. The intensity of fluorescence produced by dye-laser excitation within this absorption band was measured as a function of emission wavelength. Excitation of the longest- and shortest-wavelength absorption peaks produced identical emission profiles, but no distinct fluorescence signal was detected when the laser was tuned to the central absorption peaks, indicating that the apparent absorption triplet is actually the superposition of a singlet and a doublet absorption originating from two different trapping sites. No additional absorption bands were detected.

  12. Excited-state absorption and fluorescence dynamics of Er3+:KY3F10

    NASA Astrophysics Data System (ADS)

    Labbé, C.; Doualan, J. L.; Moncorgé, R.; Braud, A.; Camy, P.

    2018-05-01

    We report here on a complete investigation of the excited-state absorption and fluorescence dynamics of Er3+ doped KY3F10 single crystals versus dopant concentrations and optical excitation conditions. Radiative and effective (including non-radiative relaxations) emission lifetimes and branching ratios are determined from a Judd-Ofelt analysis of the absorption spectra and via specific fluorescence experiments using wavelength selective laser excitations. Excited-state absorption and emission spectra are registered within seven spectral domains, i.e. 560 nm, 650 nm, 710 nm, 810 nm, 970 nm, 1550 nm and 2750 nm. A maximum gain cross-section of 0.93 × 10-21 cm2 is determined at the potential laser wavelength of 2.801 μm for a population ratio of 0.48. Saturation of fluorescence intensities and variations of population ratios versus pumping rates are registered and confronted with a rate equation model to derive the rates of the most important up-conversion and cross-relaxation energy transfers occurring at high dopant concentrations.

  13. Combined "dual" absorption and fluorescence smartphone spectrometers.

    PubMed

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

    2015-04-15

    A combined "dual" absorption and fluorescence smartphone spectrometer is demonstrated. The optical sources used in the system are the white flash LED of the smartphone and an orthogonally positioned and interchangeable UV (λex=370  nm) and blue (λex=450  nm) LED. The dispersive element is a low-cost, nano-imprinted diffraction grating coated with Au. Detection over a 300 nm span with 0.42 nm/pixel resolution was carried out with the camera CMOS chip. By integrating the blue and UV excitation sources into the white LED circuitry, the entire system is self-contained within a 3D printed case and powered from the smartphone battery; the design can be scaled to add further excitation sources. Using a customized app, acquisition of absorption and fluorescence spectra are demonstrated using a blue-absorbing and green-emitting pH-sensitive amino-naphthalimide-based fluorescent probe and a UV-absorbing and blue-emitting Zn2+-sensitive fluoro-ionophore.

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

    NASA Astrophysics Data System (ADS)

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

    2007-05-01

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

  15. Fluorescence Spectra of Highlighter Inks

    NASA Astrophysics Data System (ADS)

    Birriel, Jennifer J.; King, Damon

    2018-01-01

    Fluorescence spectra excited by laser pointers have been the subject of several papers in TPT. These papers all describe a fluorescence phenomenon in which the reflected laser light undergoes a change in color: this color change results from the combination of some partially reflected laser light and additional colors generated by fluorescent emission. Here we examine the fluorescence spectra of highlighter inks using green and violet laser pointers. We use an RSpec Explorer spectrometer to obtain spectra and compare the emission spectra of blue, green, yellow, orange, pink, and purple highlighters. The website Compound Interest details the chemical composition of highlighter inks; in addition, the site discusses how some base dye colors can be combined to produce the variety commercially available colors. Spectra obtained in this study were qualitatively consistent with the Compound Interest site. We discuss similarities and differences between various highlighter colors and conclude with the relevance of such studies to physics students.

  16. Green synthesis, structure and fluorescence spectra of new azacyanine dyes

    NASA Astrophysics Data System (ADS)

    Enchev, Venelin; Gadjev, Nikolai; Angelov, Ivan; Minkovska, Stela; Kurutos, Atanas; Markova, Nadezhda; Deligeorgiev, Todor

    2017-11-01

    A series of symmetric and unsymmetric monomethine azacyanine dyes (monomethine azacyanine and merocyanine sulfobetaines) were synthesized with moderate to high yields via a novel method using microwave irradiation. The compounds are derived from a condensation reaction between 2-thiomethylbenzotiazolium salts and 2-imino-3-methylbenzothiazolines proceeded under microwave irradiation. The synthetic approach involves the use of green solvent and absence of basic reagent. TD-DFT calculations were performed to simulate absorption and fluorescent spectra of synthesized dyes. Absorption maxima, λmax, of the studied dyes were found in the range 364-394 nm. Molar absorbtivities were evaluated in between 40300 and 59200 mol-1 dm3 cm-1. Fluorescence maxima, λfl, were registered around 418-448 nm upon excitation at 350 nm. A slight displacements of theoretically estimated absorption maxima according to experimental ones is observed. The differences are most probably due to the fact that the DFT calculations were carried out without taking into account the solvent effect. In addition, the merocyanine sulfobetaines also fluorescence in blue optical range (420-480 nm) at excitation in red range (630-650 nm).

  17. 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

  18. 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. Copyright © 2014 Elsevier B.V. All rights reserved.

  19. Determination of the optical absorption spectra of thin layers from their photoacoustic spectra

    NASA Astrophysics Data System (ADS)

    Bychto, Leszek; Maliński, Mirosław; Patryn, Aleksy; Tivanov, Mikhail; Gremenok, Valery

    2018-05-01

    This paper presents a new method for computations of the optical absorption coefficient spectra from the normalized photoacoustic amplitude spectra of thin semiconductor samples deposited on the optically transparent and thermally thick substrates. This method was tested on CuIn(Te0.7Se0.3)2 thin films. From the normalized photoacoustic amplitude spectra, the optical absorption coefficient spectra were computed with the new formula as also with the numerical iterative method. From these spectra, the value of the energy gap of the thin film material and the type of the optical transitions were determined. From the experimental optical transmission spectra, the optical absorption coefficient spectra were computed too, and compared with the optical absorption coefficient spectra obtained from photoacoustic spectra.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lee, Hyun Ji; Laskin, Alexander; Laskin, Julia

    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)more » 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.« less

  1. 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.

  2. 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. Copyright © 2015 John Wiley & Sons, Ltd.

  3. Light Absorption and Excitation-Emission Fluorescence of Urban Organic Aerosol Components and Their Relationship to Chemical Structure.

    PubMed

    Chen, Qingcai; Ikemori, Fumikazu; Mochida, Michihiro

    2016-10-18

    The present study used a combination of solvent and solid-phase extractions to fractionate organic compounds with different polarities from total suspended particulates in Nagoya, Japan, and their optical characteristics were obtained on the basis of their UV-visible absorption spectra and excitation-emission matrices (EEMs). The relationship between their optical characteristics and chemical structures was investigated based on high-resolution aerosol mass spectra (HR-AMS spectra), soft ionization mass spectra and Fourier transform infrared (FT-IR) spectra. The major light-absorption organics were less polar organic fractions, which tended to have higher mass absorption efficiencies (MAEs) and lower wavelength dependent Ångström exponents (Å) than the more polar organic fractions. Correlation analyses indicate that organic compounds with O and N atoms may contribute largely to the total light absorption and fluorescence of the organic aerosol components. The extracts from the aerosol samples were further characterized by a classification of the EEM profiles using a PARAFAC model. Different fluorescence components in the aerosol organic EEMs were associated with specific AMS ions and with different functional groups from the FT-IR analysis. These results may be useful to determine and further classify the chromophores in atmospheric organic aerosols using EEM spectroscopy.

  4. 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

  5. Solvent effects on the fluorescence and effective three-photon absorption of a Zn(II)-[meso-tetrakis(4-octyloxyphenyl)porphyrin

    NASA Astrophysics Data System (ADS)

    Wan, Yong; Xue, Yuxiong; Sheng, Ning; Rui, Guanghao; Lv, Changgui; He, Jun; Gu, Bing; Cui, Yiping

    2018-06-01

    The fluorescence and effective three-photon absorption (3PA) properties of Zn(II)-[meso-tetrakis(4-octyloxyphenyl)porphyrin] (labeled Zn(II)-porphyrin) dissolved in three different polar solvents were systematically investigated. The electrochemical and photophysical properties of Zn(II)-porphyrin were investigated by 1H NMR spectra, IR spectra, mass spectroscopy, and electronic absorption spectra. The fluorescence emission of Zn(II)-porphyrin in three different solvents excited at the wavelengths of 420 nm (Soret band) and 550 nm (Q-band) were analyzed. By performing Z-scan experiments with femtosecond laser pulses at a wavelength of 800 nm, the effective 3PA process of Zn(II)-porphyrin in three different solvents was observed and the underlying mechanism was discussed in detail. It is found that the fluorescence spectra slightly depend on the polarity of the solvent. Interestingly, the effective 3PA properties of Zn(II)-porphyrin strongly depend on the solvent polarity. The lower the solvent polarity is, the larger effective 3PA cross-section is. Low polar solvents are beneficial to applications of Zn(II)-porphyrin in optical limiting, photodynamic therapy, etc.

  6. Comparative Studies in the Fluorescence and Excitation Spectra of 3-Hydroxyflavone and 2(2 '-Heteroaryl)-3-Hydroxy-4H-Chromen-4-Ones

    NASA Astrophysics Data System (ADS)

    Kaur, R.; Kaur, K.; Bansal, M.

    2017-05-01

    The absorption, fluorescence, and excitation spectra of FHC and THC have been studied and compared with 3HF in cyclohexane, acetonitrile, and methanol. Anion formation in acetonitrile and methanol has been observed in all three flavonols in the order THC-FHC-3HF in their ground states. As excitation and absorption spectra are similar in all the cases (including the anion one), it is possible to observe the absorption spectra of the pure anion of the flavonols in neutral solvents, which is difficult to measure directly.

  7. 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.

  8. Excitation Dynamics in Phycoerythrin 545: Modeling of Steady-State Spectra and Transient Absorption with Modified Redfield Theory

    PubMed Central

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

    2010-01-01

    Abstract 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. PMID:20643051

  9. Fluorescence Spectra of Highlighter Inks

    ERIC Educational Resources Information Center

    Birriel, Jennifer J.; King, Damon

    2018-01-01

    Fluorescence spectra excited by laser pointers have been the subject of several papers in "TPT". These papers all describe a fluorescence phenomenon in which the reflected laser light undergoes a change in color: this color change results from the combination of some partially reflected laser light and additional colors generated by…

  10. [Micro-Raman and fluorescence spectra of several agrochemicals].

    PubMed

    Xiao, Yi-lin; Zhang, Peng-xiang; Qian, Xiao-fan

    2004-05-01

    Raman and fluorescence spectra from several agrochemicals were measured, which are sold for the use in vegetables, fruits and grains. Characteristic vibration Raman peaks from some of the agrochemicals were recorded, hence the spectra can be used for their identification. Other marketed agrochemicals demonstrated strong fluorescence under 514.5 nm excitation. It was found that the fluorescence spectra of the agrochemicals are very different. According to these results one can detect the trace amount of agrochemicals left on the surface of fruits, vegetables and grains in situ and conveniently.

  11. Absorption and emission spectroscopic characterisation of 8-amino-riboflavin

    NASA Astrophysics Data System (ADS)

    Tyagi, A.; Zirak, P.; Penzkofer, A.; Mathes, T.; Hegemann, P.; Mack, M.; Ghisla, S.

    2009-10-01

    The flavin dye 8-amino-8-demethyl- D-riboflavin (AF) in the solvents water, DMSO, methanol, and chloroform/DMSO was studied by absorption and fluorescence spectroscopy. The first absorption band is red-shifted compared to riboflavin, and blue-shifted compared to roseoflavin (8-dimethylamino-8-demethyl-D-riboflavin). The fluorescence quantum yield of AF in the studied solvents varies between 20% and 50%. The fluorescence lifetimes were found to be in the 2-5 ns range. AF is well soluble in DMSO, weakly soluble in water and methanol, and practically insoluble in chloroform. The limited solubility causes AF aggregation, which was seen in differences between measured absorption spectra and fluorescence excitation spectra. Light scattering in the dye absorption region is discussed and approximate absorption cross-section spectra are determined from the combined measurement of transmission and fluorescence excitation spectra. The photo-stability of AF was studied by prolonged light exposure. The photo-degradation routes of AF are discussed.

  12. 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.

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

    PubMed

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

    2016-07-08

    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.

  14. Kα X-Ray Emission Spectra and K X-Ray Absorption-Edge Structures of Fluorine in 3d Transition-Metal Difluorides

    NASA Astrophysics Data System (ADS)

    Sugiura, Chikara

    1991-08-01

    The fluorine Kα emission spectra in fluorescence from a series of 3d transition-metal difluorides MF2 (M=Mn, Fe, Co, Ni, Cu and Zn) have been measured with a high-resolution two-crystal vacuum spectrometer. It is shown that the observed FWHM of the Kα1,2 emission band is closely related to the difference in the electronegativity between the metal and fluorine atoms. The measured emission spectra are presented along with the UPS or XPS spectra of the valence bands and the fluorine K absorption spectra of the metal difluorides, reported previously. The structures at the fluorine K absorption edges are interpreted in terms of a molecular orbital (MO) model.

  15. Two-Photon Excitation, Fluorescence Microscopy, and Quantitative Measurement of Two-Photon Absorption Cross Sections

    NASA Astrophysics Data System (ADS)

    DeArmond, Fredrick Michael

    As optical microscopy techniques continue to improve, most notably the development of super-resolution optical microscopy which garnered the Nobel Prize in Chemistry in 2014, renewed emphasis has been placed on the development and use of fluorescence microscopy techniques. Of particular note is a renewed interest in multiphoton excitation due to a number of inherent properties of the technique including simplified optical filtering, increased sample penetration, and inherently confocal operation. With this renewed interest in multiphoton fluorescence microscopy, comes an increased demand for robust non-linear fluorescent markers, and characterization of the associated tool set. These factors have led to an experimental setup to allow a systematized approach for identifying and characterizing properties of fluorescent probes in the hopes that the tool set will provide researchers with additional information to guide their efforts in developing novel fluorophores suitable for use in advanced optical microscopy techniques as well as identifying trends for their synthesis. Hardware was setup around a software control system previously developed. Three experimental tool sets were set up, characterized, and applied over the course of this work. These tools include scanning multiphoton fluorescence microscope with single molecule sensitivity, an interferometric autocorrelator for precise determination of the bandwidth and pulse width of the ultrafast Titanium Sapphire excitation source, and a simplified fluorescence microscope for the measurement of two-photon absorption cross sections. Resulting values for two-photon absorption cross sections and two-photon absorption action cross sections for two standardized fluorophores, four commercially available fluorophores, and ten novel fluorophores are presented as well as absorption and emission spectra.

  16. 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.

  17. 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

  18. A new high selective and sensitive turn-on fluorescent and ratiometric absorption chemosensor for Cu2+ based on benzimidazole in aqueous solution and its application in live cell.

    PubMed

    Bing, Qijing; Wang, Lin; Li, Donglin; Wang, Guang

    2018-09-05

    A new benzimidazole base turn-on fluorescent and ratiometric absorption chemosensor (L) bearing bidentate ligand for detection of Cu 2+ was designed and synthesized. Fluorescence and UV-vis spectra studies demonstrated that L can detect Cu 2+ ions in aqueous solution using fluorescence enhancement and ratiometric absorption sensing over a wide pH range. Both fluorescent and ratiometric absorption sensing of L for Cu 2+ possessed high selectivity and sensitivity over other competitive metal ions and had low detection limit. Job's plot, mass spectra and DFT calculation indicated the sensing mechanism is the complex formation between L and Cu 2+ with 1:2 stoichiometry. Fluorescence images of HepG2 in the absence and presence of Cu 2+ displayed L had cell permeability and detection ability for Cu 2+ in live cells. Copyright © 2018 Elsevier B.V. All rights reserved.

  19. 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

  20. Rich magneto-absorption spectra of AAB-stacked trilayer graphene.

    PubMed

    Do, Thi-Nga; Shih, Po-Hsin; Chang, Cheng-Peng; Lin, Chiun-Yan; Lin, Ming-Fa

    2016-06-29

    A generalized tight-binding model is developed to investigate the feature-rich magneto-optical properties of AAB-stacked trilayer graphene. Three intragroup and six intergroup inter-Landau-level (inter-LL) optical excitations largely enrich magneto-absorption peaks. In general, the former are much higher than the latter, depending on the phases and amplitudes of LL wavefunctions. The absorption spectra exhibit single- or twin-peak structures which are determined by quantum modes, LL energy spectra and Fermion distribution. The splitting LLs, with different localization centers (2/6 and 4/6 positions in a unit cell), can generate very distinct absorption spectra. There exist extra single peaks because of LL anti-crossings. AAB, AAA, ABA, and ABC stackings considerably differ from one another in terms of the inter-LL category, frequency, intensity, and structure of absorption peaks. The main characteristics of LL wavefunctions and energy spectra and the Fermi-Dirac function are responsible for the configuration-enriched magneto-optical spectra.

  1. 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. Copyright © 2014 Elsevier Ltd. All rights reserved.

  2. Novel push-pull fluorescent dyes - 7-(diethylamino)furo- and thieno[3,2-c]coumarins derivatives: structure, electronic spectra and TD-DFT study

    NASA Astrophysics Data System (ADS)

    Akchurin, Igor O.; Yakhutina, Anna I.; Bochkov, Andrei Y.; Solovjova, Natalya P.; Medvedev, Michael G.; Traven, Valerii F.

    2018-05-01

    Novel push-pull fluorescent dyes - 7-(diethylamino)furo- and 7-(diethylamino)thieno[3,2-c]coumarins derivatives have been synthesized using formyl derivatives of furo- and thieno[3,2-c]coumarins as starting materials. Electron absorption and fluorescent spectra of the dyes have been recorded in different solvents. Structure and solvent effects on the dyes spectral characteristics were analyzed. The fusion of five-membered heterocycle to coumarin provides a definite increase of Stokes shifts in all solvents and results in higher quantum yields of fluorescence. The absorption and emission bands of thieno[3,2-c] coumarin derivatives are definitely shifted to the red region (3-30 nm) compared to similar derivatives of furo[3,2-c]coumarin. TD-DFT calculations of some of the studied compounds have shown that hybrid DFT functionals and adequate representation of molecular environment are essential for obtaining accurate UV-Vis absorption spectra for the dyes with extended π-system. The longest-wave electron transitions in the studied compounds were computationally shown to be of push-pull nature.

  3. Creating semiconductor metafilms with designer absorption spectra

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kim, Soo Jin; Fan, Pengyu; Kang, Ju-Hyung

    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 thatmore » 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.« less

  4. Electron and fluorescence spectra of a water molecule irradiated by an x-ray free-electron laser pulse

    NASA Astrophysics Data System (ADS)

    Schäfer, Julia M.; Inhester, Ludger; Son, Sang-Kil; Fink, Reinhold F.; Santra, Robin

    2018-05-01

    With the highly intense x-ray light generated by x-ray free-electron lasers (XFELs), molecular samples can be ionized many times in a single pulse. Here we report on a computational study of molecular spectroscopy at the high x-ray intensity provided by XFELs. Calculated photoelectron, Auger electron, and x-ray fluorescence spectra are presented for a single water molecule that reaches many electronic hole configurations through repeated ionization steps. The rich details shown in the spectra depend on the x-ray pulse parameters in a nonintuitive way. We discuss how the observed trends can be explained by the competition of microscopic electronic transition processes. A detailed comparison between spectra calculated within the independent-atom model and within the molecular-orbital framework highlights the chemical sensitivity of the spectral lines of multiple-hole configurations. Our results demonstrate how x-ray multiphoton ionization-related effects such as charge-rearrangement-enhanced x-ray ionization of molecules and frustrated absorption manifest themselves in the electron and fluorescence spectra.

  5. Spectroscopic identification of individual fluorophores using photoluminescence excitation spectra.

    PubMed

    Czerski, J; Colomb, W; Cannataro, F; Sarkar, S K

    2018-01-25

    The identity of a fluorophore can be ambiguous if other fluorophores or nonspecific fluorescent impurities have overlapping emission spectra. The presence of overlapping spectra makes it difficult to differentiate fluorescent species using discrete detection channels and unmixing of spectra. The unique absorption and emission signatures of fluorophores provide an opportunity for spectroscopic identification. However, absorption spectroscopy may be affected by scattering, whereas fluorescence emission spectroscopy suffers from signal loss by gratings or other dispersive optics. Photoluminescence excitation spectra, where excitation is varied and emission is detected at a fixed wavelength, allows hyperspectral imaging with a single emission filter for high signal-to-background ratio without any moving optics on the emission side. We report a high throughput method for measuring the photoluminescence excitation spectra of individual fluorophores using a tunable supercontinuum laser and prism-type total internal reflection fluorescence microscope. We used the system to measure and sort the photoluminescence excitation spectra of individual Alexa dyes, fluorescent nanodiamonds (FNDs), and fluorescent polystyrene beads. We used a Gaussian mixture model with maximum likelihood estimation to objectively separate the spectra. Finally, we spectroscopically identified different species of fluorescent nanodiamonds with overlapping spectra and characterized the heterogeneity of fluorescent nanodiamonds of varying size. © 2018 The Authors Journal of Microscopy © 2018 Royal Microscopical Society.

  6. Polarized two-photon fluorescence excitation spectra of indole and benzimidazole

    NASA Astrophysics Data System (ADS)

    Anderson, Bruce E.; Jones, Richard D.; Rehms, Aden A.; Ilich, Predrag; Callis, Patrik R.

    1986-03-01

    Polarized two-photon fluorescence excitation spectra of indole in hexane, benzimidazole in isopropanol, and benzimidazole cation in methanol-H 2SO 4, all at 0.2 M and 25°C are reported for the excitation range 470-600 nm, the region of their L b, and L a bands. Relative two-photon absorptivities are deduced by correcting for different fluorescence response and are compared to toluene's L b band. The indole integrated absorptivity is about 10 times greater than that of toluene. The L a band of indole appears less dominant than in one-photon but still outweighs the L b band by a factor of 4. The two-photon polarization spectrum for indole indicates that the L a origin lies ≈500-1000 cm -1 above the L b origin in hexane. The benzimidazoles absorb only about twice as strongly as toluene and show strong vibronic peaks; the L a, bands are only faintly seen. Two-photon properties calculated from INDO/S CI wavefunctions with doubly excited configurations are in good agreement with those of indole, but predict the benzimidazole TPA to be several times stronger than observed. For the cation, the predicted results are nearly two orders of magnitude too high.

  7. 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.

  8. Efficiency of the intermolecular interaction of salicylic acid neutral form and monoanion with Cd2 + ion studied by methods of absorption and fluorescence

    NASA Astrophysics Data System (ADS)

    Lavrik, N. L.; Mulloev, N. U.

    2018-02-01

    The methods of absorption and fluorescence were used to study the efficiency of the interaction between salicylic acid derivatives SAD (neutral SA form and SA monoanion) and Cd2 + ions (in CdBr2 salt) within the range pH = 1.5 ÷ 8. The efficiency was determined from the change in both the absorption band contour and the fluorescence intensity of various SAD forms. It has been established that depending on the SAD form, the addition of CdBr2 to a starting solution leads to the formation of additional absorption for both the shorter wave lengths in the absorption spectrum of the neutral form (at pH < 3) and the longer wave lengths in the absorption spectrum for the HSal- monoanion (at pH > 4). In the fluorescence spectra, the intensity was observed to increase for the neutral SAD form (at pH < 3) and to decrease for the HSal- monoanion (at pH > 4) after addition of CdBr2. The spectral changes were interpreted in the framework of common notions about the effect of three physicochemical factors that determine the interaction between the SAD and the Cd2 + ion and affect the parameters of absorption and fluorescence spectra. These factors are: (1) the decrease in pH after addition of CdBr2 to the SAD solution, (2) the decrease in the efficiency of the H-bonding of SAD molecules to the water ones, and (3) the existence of electrostatic ion-ion interaction between the HSal- monoanion and the Cd2 + ion. The bimolecular fluorescence quenching constants Kq of HSal- monoanion fluorescence quenching by the Cd2 + ion appeared to be substantially less than those of the quenching which would follow either the dynamic (diffusion) or the concentration (static) mechanisms.

  9. Soft x-ray absorption spectra of ilmenite family.

    PubMed

    Agui, A; Mizumaki, M; Saitoh, Y; Matsushita, T; Nakatani, T; Fukaya, A; Torikai, E

    2001-03-01

    We have carried out soft x-ray absorption spectroscopy to study the electronic structure of ilmenite family, such as MnTiO3, FeTiO3, and CoTiO3 at the soft x-ray beamline, BL23SU, at the SPring-8. The Ti and M L2,3 absorption spectra of MTiO3 (M=Mn, Fe, and Co) show spectra of Ti4+ and M2+ electron configurations, respectively. Except the Fe L2,3 spectrum, those spectra were understood within the O(h) symmetry around the transition metal ions. The Fe L3-edge spectrum clearly shows a doublet peak at the L3 edge, which is attributed to Fe2+ state, moreover the very high-resolution the L-edge spectra of transition metals show fine structures. The spectra of those ilmenites are compared.

  10. 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

  11. Gritty Surface Sample Holder Invented To Obtain Correct X-ray Absorption Fine Structure Spectra for Concentrated Materials by Fluorescence Yield.

    PubMed

    Abe, Hitoshi; Niwa, Yasuhiro; Kimura, Masao; Murakami, Youichi; Yokoyama, Toshiharu; Hosono, Hideo

    2016-04-05

    A gritty surface sample holder has been invented to obtain correct XAFS spectra for concentrated samples by fluorescence yield (FY). Materials are usually mixed with boron nitride (BN) to prepare proper concentrations to measure XAFS spectra. Some materials, however, could not be mixed with BN and would be measured in too concentrated conditions to obtain correct XAFS spectra. Consequently, XAFS spectra will be incorrect typically with decreased intensities of the peaks. We have invented the gritty surface sample holders to obtain correct XAFS spectra even for concentrated materials for FY measurements. Pure Cu and CuO powders were measured mounted on the sample holders, and the same spectra were obtained as transmission spectra of properly prepared samples. This sample holder is useful to measure XAFS for any concentrated materials.

  12. 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.

  13. 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.

    PubMed

    Kityk, A V

    2014-07-15

    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. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. Gigahertz-peaked Spectra Pulsars and Thermal Absorption Model

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kijak, J.; Basu, R.; Lewandowski, W.

    2017-05-10

    We present the results of our radio interferometric observations of pulsars at 325 and 610 MHz using the Giant Metrewave Radio Telescope. We used the imaging method to estimate the flux densities of several pulsars at these radio frequencies. The analysis of the shapes of the pulsar spectra allowed us to identify five new gigahertz-peaked spectra (GPS) pulsars. Using the hypothesis that the spectral turnovers are caused by thermal free–free absorption in the interstellar medium, we modeled the spectra of all known objects of this kind. Using the model, we were able to put some observational constraints on the physicalmore » parameters of the absorbing matter, which allows us to distinguish between the possible sources of absorption. We also discuss the possible effects of the existence of GPS pulsars on future search surveys, showing that the optimal frequency range for finding such objects would be from a few GHz (for regular GPS sources) to possibly 10 GHz for pulsars and radio magnetars exhibiting very strong absorption.« less

  15. 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. Copyright © 2016 Elsevier B.V. All rights reserved.

  16. Theoretical Prediction of Si 2–Si 33 Absorption Spectra

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhao, Li -Zhen; Lu, Wen -Cai; Qin, Wei

    Here, the optical absorption spectra of Si 2–Si 33 clusters were systematically studied by a time-dependent density functional theory approach. The calculations revealed that the absorption spectrum becomes significantly broad with increasing cluster size, stretching from ultraviolet to the infrared region. The absorption spectra are closely related to the structural motifs. With increasing cluster size, the absorption intensity of cage structures gradually increases, but the absorption curves of the prolate and the Y-shaped structures are very sensitive to cluster size. If the transition energy reaches ~12 eV, it is noted that all the clusters have remarkable absorption in deep ultravioletmore » region of 100–200 nm, and the maximum absorption intensity is ~100 times that in the visible region. Further, the optical responses to doping in the Si clusters were studied.« less

  17. Theoretical Prediction of Si 2–Si 33 Absorption Spectra

    DOE PAGES

    Zhao, Li -Zhen; Lu, Wen -Cai; Qin, Wei; ...

    2017-07-07

    Here, the optical absorption spectra of Si 2–Si 33 clusters were systematically studied by a time-dependent density functional theory approach. The calculations revealed that the absorption spectrum becomes significantly broad with increasing cluster size, stretching from ultraviolet to the infrared region. The absorption spectra are closely related to the structural motifs. With increasing cluster size, the absorption intensity of cage structures gradually increases, but the absorption curves of the prolate and the Y-shaped structures are very sensitive to cluster size. If the transition energy reaches ~12 eV, it is noted that all the clusters have remarkable absorption in deep ultravioletmore » region of 100–200 nm, and the maximum absorption intensity is ~100 times that in the visible region. Further, the optical responses to doping in the Si clusters were studied.« less

  18. 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; Suresh Kumar, H M; 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. Copyright © 2015. Published by Elsevier B.V.

  19. [Fluorescence spectra analysis of the scrophularia soup].

    PubMed

    Yan, Li-hua; Song, Feng; Han, Juan; Su, Jing; Qu, Fei-fei; Song, Yi-zhan; Hu, Bo-lin; Tian, Jian-guo

    2008-08-01

    The cold-water and boiled-water soaked scrophularia soups have been prepared. The emission and excitation spectra of each scrophularia soup under different conditions have been measured at room temperature. The pH values of the different scrophularia soups have been also detected. There are obvious differences between the cold-water soaked scrophularia soup and the boiled-water soaked scrophularia. For both soups the emission wavelength increases with the wavelength of the excitation, but the peaks of the emission spectra for cold-water and boiled-water soaked scrophularia soup are different, which are 441 and 532 nm, respectively. Excitation spectrum has double peaks in the cold-water soaked scrophularia soup while only one peak with longer wavelength in the boiled-water soaked one. The pH value changes from 5.5 to 4.1. According to the organic admixture fluorescence mechanism we analyzed the reasons of the experimental results. Through heating, the interaction in different fluorescence molecular and the energy transfer process in the same fluorescence molecular become more active, and the conjugate structures and the generation of hydrogen bonds, increase. The fluorescence measurement is of value for the scrophularia pharmacology analysis and provides an analytical method for the quality identification of scrophularia soup.

  20. 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.

  1. First-principles C band absorption spectra of SO2 and its isotopologues

    NASA Astrophysics Data System (ADS)

    Jiang, Bin; Kumar, Praveen; Kłos, Jacek; Alexander, Millard H.; Poirier, Bill; Guo, Hua

    2017-04-01

    The low-energy wing of the C ˜ B12 ←X˜ 1A1 absorption spectra for SO2 in the ultraviolet region is computed for the 32S,33S,34S and 36S isotopes, using the recently developed ab initio potential energy surfaces (PESs) of the two electronic states and the corresponding transition dipole surface. The state-resolved absorption spectra from various ro-vibrational states of SO2(X˜ 1A1 ) are computed. When contributions of these excited ro-vibrational states are included, the thermally averaged spectra are broadened but maintain their key characters. Excellent agreement with experimental absorption spectra is found, validating the accuracy of the PESs. The isotope shifts of the absorption peaks are found to increase linearly with energy, in good agreement with experiment.

  2. 2D fluorescence spectra measurement of six kinds of bioagents simulants by short range Lidar

    NASA Astrophysics Data System (ADS)

    Sanpedro, Man

    2018-02-01

    Pantoea agglomerans (Pan), Staphylococcus aureus (Sta), Bacillus globigii (BG) and Escherichia coli (EH), these four kinds of bioagents simulants of were cultured and then their growth curves were measured, the generation time was 0.99h, 0.835h, 1.07h and 1.909h, respectively. A small short range fluorescence lidar working at wavelengths of 266nm and 355nm was designed and used to measure the two-dimensional fluorescence spectra of bioagents simulants in the amino acid segment and NADH segment, respectively. In a controllable fluorescence measurement chamber, the two-dimensional fluorescence spectra of vegetative liquid bacterial aerosols as well as BSA and OVA, two protein toxinic simulants were measured with a resolution of 4nm. The two-dimensional fluorescence spectral shape of Pan, Sta, EH and BG, BSA and OVA were consistent with the standard fluorescent component tryptophan in the amino acid band with FWHM of 60nm, but the central wavelength of the fluorescence spectra of these simulants blue/purple shifted obviously as affected by the external biochemical environment, concentration and ratio of different bacterial internal fluorophores, so the energy level between the excited state and the ground state of the fluorescence molecule increased. Differently, weak NADH fluorescence spectra with 100nm FWHM inside the four vegetative bacteria aerosols were detected, but Rayleigh scattering, Raman scattering contribution of water, nitrogen in the fluorescence spectra could not be effectively extracted. The second - order derivative fluorescence spectra of four simulants showed that the high - order processing and recognition of the fluorescence spectra was feasible.

  3. 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.

  4. Two-photon absorption spectra of carotenoids compounds

    NASA Astrophysics Data System (ADS)

    Vivas, Marcelo Gonçalves; Silva, Daniel Luiz; Boni, Leonardo de; Zalesny, Robert; Bartkowiak, Wojciech; Mendonca, Cleber Renato

    2011-05-01

    Carotenoids are biosynthetic organic pigments that constitute an important class of one-dimensional π-conjugated organic molecules with enormous potential for application in biophotonic devices. In this context, we studied the degenerate two-photon absorption (2PA) cross-section spectra of two carotenoid compounds (β-carotene and β-apo-8'-carotenal) employing the conventional and white-light-continuum Z-scan techniques and quantum chemistry calculations. Because carotenoids coexist at room temperature as a mixture of isomers, the 2PA spectra reported here are due to samples containing a distribution of isomers, presenting distinct conjugation length and conformation. We show that these compounds present a defined structure on the 2PA spectra, that peaks at 650 nm with an absorption cross-section of approximately 5000 GM, for both compounds. In addition, we observed a 2PA band at 990 nm for β-apo-8'-carotenal, which was attributed to a overlapping of 11Bu+-like and 21Ag--like states, which are strongly one- and two-photon allowed, respectively. Spectroscopic parameters of the electronic transitions to singlet-excited states, which are directly related to photophysical properties of these compounds, were obtained by fitting the 2PA spectra using the sum-over-states approach. The analysis and interpretations of the 2PA spectra of the investigated carotenoids were supported by theoretical predictions of one- and two-photon transitions carried out using the response functions formalism within the density functional theory framework, using the long-range corrected CAM-B3LYP functional.

  5. 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

  6. 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

  7. Substituent and solvent effects on electronic absorption spectra of some N-(substitutedphenyl)benzene sulphonamides

    NASA Astrophysics Data System (ADS)

    Suganya, Krishnasamy; Kabilan, Senthamaraikannan

    2004-04-01

    The effects of substituents and solvents have been studied through the absorption spectra of nearly 23 ortho- and para-N-(substitutedphenyl)benzene sulphonamides in the range of 200-400 nm. The effects of substituents on the absorption spectra of compounds under present investigation are interpreted by correlation of absorption frequencies with simple and extended Hammett equations. Effect of solvent polarity and hydrogen bonding on the absorption spectra are interpreted by means of Kamlet equation and the results are discussed.

  8. Absorption Spectra of Gold Nanoparticle Suspensions

    NASA Astrophysics Data System (ADS)

    Anan'eva, M. V.; Nurmukhametov, D. R.; Zverev, A. S.; Nelyubina, N. V.; Zvekov, A. A.; Russakov, D. M.; Kalenskii, A. V.; Eremenko, A. N.

    2018-02-01

    Three gold nanoparticle suspensions are obtained, and mean radii in distributions - (6.1 ± 0.2), (11.9 ± 0.3), and (17.3 ± 0.7) nm - are determined by the transmission electron microscopy method. The optical absorption spectra of suspensions are obtained and studied. Calculation of spectral dependences of the absorption index of suspensions at values of the gold complex refractive index taken from the literature showed a significant deviation of experimental and calculated data in the region of 450-800 nm. Spectral dependences of the absorption of suspensions are simulated within the framework of the Mie-Drude theory taking into account the interband absorption in the form of an additional term in the imaginary part of the dielectric permittivity of the Gaussian type. It is shown that to quantify the spectral dependences in the region of the plasmon absorption band of nanoparticles, correction of the parameters of the interband absorption is necessary in addition to the increase of the relaxation parameter of the Drude theory. Spectral dependences of the dielectric permittivity of gold in nanodimensional state are refined from the solution of the inverse problem. The results of the present work are important for predicting the special features of operation of photonic devices and optical detonators based on gold nanoparticles.

  9. Substituent and solvent effects on electronic absorption spectra of some N-(substitutedphenyl)benzene sulphonamides.

    PubMed

    Suganya, Krishnasamy; Kabilan, Senthamaraikannan

    2004-04-01

    The effects of substituents and solvents have been studied through the absorption spectra of nearly 23 ortho- and para-N-(substitutedphenyl)benzene sulphonamides in the range of 200-400 nm. The effects of substituents on the absorption spectra of compounds under present investigation are interpreted by correlation of absorption frequencies with simple and extended Hammett equations. Effect of solvent polarity and hydrogen bonding on the absorption spectra are interpreted by means of Kamlet equation and the results are discussed. Copyright 2003 Elsevier B.V.

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

    PubMed

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

    2007-07-01

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

  11. 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

  12. Emission spectra profiling of fluorescent proteins in living plant cells

    PubMed Central

    2013-01-01

    Background Fluorescence imaging at high spectral resolution allows the simultaneous recording of multiple fluorophores without switching optical filters, which is especially useful for time-lapse analysis of living cells. The collected emission spectra can be used to distinguish fluorophores by a computation analysis called linear unmixing. The availability of accurate reference spectra for different fluorophores is crucial for this type of analysis. The reference spectra used by plant cell biologists are in most cases derived from the analysis of fluorescent proteins in solution or produced in animal cells, although these spectra are influenced by both the cellular environment and the components of the optical system. For instance, plant cells contain various autofluorescent compounds, such as cell wall polymers and chlorophyll, that affect the spectral detection of some fluorophores. Therefore, it is important to acquire both reference and experimental spectra under the same biological conditions and through the same imaging systems. Results Entry clones (pENTR) of fluorescent proteins (FPs) were constructed in order to create C- or N-terminal protein fusions with the MultiSite Gateway recombination technology. The emission spectra for eight FPs, fused C-terminally to the A- or B-type cyclin dependent kinases (CDKA;1 and CDKB1;1) and transiently expressed in epidermal cells of tobacco (Nicotiana benthamiana), were determined by using the Olympus FluoView™ FV1000 Confocal Laser Scanning Microscope. These experimental spectra were then used in unmixing experiments in order to separate the emission of fluorophores with overlapping spectral properties in living plant cells. Conclusions Spectral imaging and linear unmixing have a great potential for efficient multicolor detection in living plant cells. The emission spectra for eight of the most commonly used FPs were obtained in epidermal cells of tobacco leaves and used in unmixing experiments. The generated set of

  13. Fluorescence spectral properties of stomach tissues with pathology

    NASA Astrophysics Data System (ADS)

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

    2012-05-01

    Steady-state fluorescence and diffuse reflection spectra are measured for in vivo normal and pathological (chronic atrophic and ulcerating defects, malignant neoplasms) stomach mucous lining tissues. The degree of distortion of the fluorescence spectra is estimated taking light scattering and absorption into account. A combination of Gauss and Lorentz functions is used to decompose the fluorescence spectra. Potential groups of fluorophores are determined and indices are introduced to characterize the dynamics of their contributions to the resultant spectra as pathologies develop. Reabsorption is found to quench the fluorescence of structural proteins by as much as a factor of 3, while scattering of the light can increase the fluorescence intensity of flavin and prophyrin groups by as much as a factor of 2.

  14. One trinucleus dimethine cyanine dye: Experimental and theoretical studies on molecular structure as well as absorption and fluorescence properties

    NASA Astrophysics Data System (ADS)

    Zhang, D. D.; Wang, L. Y.; Su, J. J.; Zhang, X. F.; Lei, Y. B.; Zhai, G. H.; Wen, Z. Y.

    2013-05-01

    A kind of trinucleus dimethine cyanine dye: 1-methyl-2,6-bis[2-(furan-2-yl)vinyl]pyridinium iodide (1) was synthesized and characterized by 1H NMR, 13C NMR, IR, MS, UV-Vis spectroscopy and elemental analysis. The crystals of dye 1, obtained from slow evaporation of solvent acetone, crystallized in the triclinic space group P - 1 with a = 9.6501(16) Å, b = 10.2308(17) Å, c = 10.7341(17) Å, V = 887.2(3) Å3, and Z = 2 (at 298(2) K), and it was stabilized by the hydrogen bonds and intermolecular face-to-face π⋯π aromatic stacking interactions. Crystallographic, IR, 1H NMR and UV-Vis data of dye 1 were compared with the results of density functional theory (DFT) method, and the calculated molecular geometries, vibrational bands, 1H NMR chemical shifts and UV-Vis maximum absorption were consistent with the experimental results. The fluorescence spectra were predicted in four different solvents with CIS/PCM methods. Compared with experimental values, the absolute deviations of emission maxima were -17.4 nm in chloroform, 6.3 nm in DMSO, 4.9 nm in methanol, and 6.8 nm in water, respectively. And the experimental fluorescence spectra were nicely reproduced by the simulated fluorescence spectra for each solvent.

  15. Automated generation and ensemble-learned matching of X-ray absorption spectra

    NASA Astrophysics Data System (ADS)

    Zheng, Chen; Mathew, Kiran; Chen, Chi; Chen, Yiming; Tang, Hanmei; Dozier, Alan; Kas, Joshua J.; Vila, Fernando D.; Rehr, John J.; Piper, Louis F. J.; Persson, Kristin A.; Ong, Shyue Ping

    2018-12-01

    X-ray absorption spectroscopy (XAS) is a widely used materials characterization technique to determine oxidation states, coordination environment, and other local atomic structure information. Analysis of XAS relies on comparison of measured spectra to reliable reference spectra. However, existing databases of XAS spectra are highly limited both in terms of the number of reference spectra available as well as the breadth of chemistry coverage. In this work, we report the development of XASdb, a large database of computed reference XAS, and an Ensemble-Learned Spectra IdEntification (ELSIE) algorithm for the matching of spectra. XASdb currently hosts more than 800,000 K-edge X-ray absorption near-edge spectra (XANES) for over 40,000 materials from the open-science Materials Project database. We discuss a high-throughput automation framework for FEFF calculations, built on robust, rigorously benchmarked parameters. FEFF is a computer program uses a real-space Green's function approach to calculate X-ray absorption spectra. We will demonstrate that the ELSIE algorithm, which combines 33 weak "learners" comprising a set of preprocessing steps and a similarity metric, can achieve up to 84.2% accuracy in identifying the correct oxidation state and coordination environment of a test set of 19 K-edge XANES spectra encompassing a diverse range of chemistries and crystal structures. The XASdb with the ELSIE algorithm has been integrated into a web application in the Materials Project, providing an important new public resource for the analysis of XAS to all materials researchers. Finally, the ELSIE algorithm itself has been made available as part of veidt, an open source machine-learning library for materials science.

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

    PubMed Central

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

    2010-01-01

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

  17. Unified analysis of optical absorption spectra of carotenoids based on a stochastic model.

    PubMed

    Uragami, Chiasa; Saito, Keisuke; Yoshizawa, Masayuki; Molnár, Péter; Hashimoto, Hideki

    2018-05-03

    The chemical structures of the carotenoid molecules are very simple and one might think that the electronic feature of it is easily predicted. However, it still has so much unknown information except the correlation between the electronic energy state and the length of effective conjugation chain of carotenoids. To investigate the electronic feature of the carotenoids, the most essential method is measuring the optical absorption spectra, but simulating it from the resonance Raman spectra is also the effective way. From this reason, we studied the optical absorption spectra as well as resonance Raman spectra of 15 different kinds of cyclic carotenoid molecules, recorded in tetrahydrofuran (THF) solutions at room temperature. The whole band shapes of the absorption spectra of all these carotenoid molecules were successfully simulated based on a stochastic model using Brownian oscillators. The parameters obtained from the simulation made it possible to discuss the intermolecular interaction between carotenoids and solvent THF molecules quantitatively. Copyright © 2018. Published by Elsevier Inc.

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

    PubMed

    Vilas, F; Gaffey, M J

    1989-11-10

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

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

    NASA Technical Reports Server (NTRS)

    Vilas, Faith; Gaffey, Michael J.

    1989-01-01

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

  20. Underdetermined blind separation of three-way fluorescence spectra of PAHs in water

    NASA Astrophysics Data System (ADS)

    Yang, Ruifang; Zhao, Nanjing; Xiao, Xue; Zhu, Wei; Chen, Yunan; Yin, Gaofang; Liu, Jianguo; Liu, Wenqing

    2018-06-01

    In this work, underdetermined blind decomposition method is developed to recognize individual components from the three-way fluorescent spectra of their mixtures by using sparse component analysis (SCA). The mixing matrix is estimated from the mixtures using fuzzy data clustering algorithm together with the scatters corresponding to local energy maximum value in the time-frequency domain, and the spectra of object components are recovered by pseudo inverse technique. As an example, using this method three and four pure components spectra can be blindly extracted from two samples of their mixture, with similarities between resolved and reference spectra all above 0.80. This work opens a new and effective path to realize monitoring PAHs in water by three-way fluorescence spectroscopy technique.

  1. 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.

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

    USGS Publications Warehouse

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

    2003-01-01

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

  3. Laser induced fluorescence of dental caries

    NASA Technical Reports Server (NTRS)

    Albin, S.; Byvik, C. E.; Buoncristiani, A. M.

    1988-01-01

    Significant differences between the optical spectra taken from sound regions of teeth and carious regions have been observed. These differences appear both in absorption and in laser induced fluorescence spectra. Excitation by the 488 nm line of an argon ion laser beam showed a peak in the emission intensity around 553 nm for the sound dental material while the emission peak from the carious region was red-shifted by approximately 40 nm. The relative absorption of carious region was significantly higher at 488 nm; however its fluorescence intensity peak was lower by an order of magnitude compared to the sound tooth. Implications of these results for a safe, reliable and early detection of dental caries are discussed.

  4. 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.

  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. 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.

  7. Underdetermined blind separation of three-way fluorescence spectra of PAHs in water.

    PubMed

    Yang, Ruifang; Zhao, Nanjing; Xiao, Xue; Zhu, Wei; Chen, Yunan; Yin, Gaofang; Liu, Jianguo; Liu, Wenqing

    2018-06-15

    In this work, underdetermined blind decomposition method is developed to recognize individual components from the three-way fluorescent spectra of their mixtures by using sparse component analysis (SCA). The mixing matrix is estimated from the mixtures using fuzzy data clustering algorithm together with the scatters corresponding to local energy maximum value in the time-frequency domain, and the spectra of object components are recovered by pseudo inverse technique. As an example, using this method three and four pure components spectra can be blindly extracted from two samples of their mixture, with similarities between resolved and reference spectra all above 0.80. This work opens a new and effective path to realize monitoring PAHs in water by three-way fluorescence spectroscopy technique. Copyright © 2018 Elsevier B.V. All rights reserved.

  8. Estimating the Biodegradability of Treated Sewage Samples Using Synchronous Fluorescence Spectra

    PubMed Central

    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. PMID:22164023

  9. 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.

  10. Excitation and fluorescence spectra of pyrene cooled in a syupersonic jet

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Borisevich, N.A.; Vodovatov, L.B.; D`yachenko, G.G.

    1995-02-01

    The excitation and fluorescence spectra of pyrene molecules cooled in a jet are obtained upon excitation into the S{sub 1}, S{sub 2}, S{sub 3}, and S{sub 4} electronic states. Based on the K. Ohno MO/8 model, a new method for calculating frequencies of the in-plane vibrations in the excited electronic states of polycyclic aromatic hydrocarbons is developed. The method is used for a comparitive analysis of the excitation and fluorescence spectra and assignment of the spectral lines. Good agreement between calculations and experimental data are found. The fluorescence spectrum recorded upon excitation into the high-lying electronic states shows a newmore » long-wavelength band that is probably related to pyrene dimers formed in a jet. 12 refs., 4 figs., 2 tabs.« less

  11. Fluorescence Spectra of Individual Flowing Airborne Biological Particles Measured in Real Time

    DTIC Science & Technology

    2001-02-01

    and fungal spores ( Aspergillus versicolor, ATCC 9577). B. subtilis var. niger (lyophilized cells) and E. herbicola were grown by streak- ing onto...Excitation Figure 7 shows fluorescence spectra of B. subtilis var. niger vegetative cells and fungal spores ( Aspergillus versicolor), both 5 µm in diameter...µm-diam clusters of B. subtilis var. niger spores, and B. subtilis var. niger vegetative cells ……………………………………… 10 5. Fluorescence spectra of starved

  12. 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.

  13. Estimating the leaf nitrogen content of paddy rice by using the combined reflectance and laser-induced fluorescence spectra.

    PubMed

    Yang, Jian; Du, Lin; Sun, Jia; Zhang, Zhenbing; Chen, Biwu; Shi, Shuo; Gong, Wei; Song, Shalei

    2016-08-22

    Paddy rice is one of the most important crops in China, and leaf nitrogen content (LNC) serves as a significant indictor for monitoring crop status. A reliable method is needed for precise and fast quantification of LNC. Laser-induced fluorescence (LIF) technology and reflectance spectra of crops are widely used to monitor leaf biochemical content. However, comparison between the fluorescence and reflectance spectra has been rarely investigated in the monitoring of LNC. In this study, the performance of the fluorescence and reflectance spectra for LNC estimation was discussed based on principal component analysis (PCA) and back-propagation neural network (BPNN). The combination of fluorescence and reflectance spectra was also proposed to monitor paddy rice LNC. The fluorescence and reflectance spectra exhibited a high degree of multi-collinearity. About 95.38%, and 97.76% of the total variance included in the spectra were efficiently extracted by using the first three PCs in PCA. The BPNN was implemented for LNC prediction based on new variables calculated using PCA. The experimental results demonstrated that the fluorescence spectra (R2 = 0.810, 0.804 for 2014 and 2015, respectively) are superior to the reflectance spectra (R2 = 0.721, 0.671 for 2014 and 2015, respectively) for estimating LNC based on the PCA-BPNN model. The proposed combination of fluorescence and reflectance spectra can greatly improve the accuracy of LNC estimation (R2 = 0.912, 0.890 for 2014 and 2015, respectively).

  14. Picosecond time-resolved absorption and fluorescence dynamics in the artificial bacteriorhodopsin pigment BR6.11.

    PubMed

    Brack, T L; Delaney, J K; Atkinson, G H; Albeck, A; Sheves, M; Ottolenghi, M

    1993-08-01

    The picosecond molecular dynamics in an artificial bacteriorhodopsin (BR) pigment containing a structurally modified all-trans retinal chromphore with a six-membered ring bridging the C11=C12-C13 positions (BR6.11) are measured by picosecond transient absorption and picosecond time-resolved fluorescence spectroscopy. Time-dependent intensity and spectral changes in absorption in the 570-650-nm region are monitored for delays as long as 5 ns after the 7-ps, 573-nm excitation of BR6.11. Two intermediates, J6.11 and K6.11/1, both with enhanced absorption to the red (> 600 nm) of the BR6.11 spectrum are observed within approximately 50 ps. The J6.11 intermediate decays with a time constant of 12 +/- 3 ps to form K6.11/1. The K6.11/1 intermediate decays with an approximately 100-ps time constant to form a third intermediate, K6.11/2, which is observed through diminished 650-nm absorption (relative to that of K6.11/1). No other transient absorption changes are found during the remainder of the initial 5-ns period of the BR6.11 photoreaction. Fluorescence in the 650-900-nm region is observed from BR6.11, K6.11/1, and K6.11/2, but no emission assignable to J6.11 is found. The BR6.11 fluroescence spectrum has a approximately 725-nm maximum which is blue-shifted by approximately 15 nm relative to that of native BR-570 and is 4.2 +/- 1.5 times larger in intensity (same sample optical density). No differences in the profile of the fluorescence spectra of BR6.11 and the intermediates K6.11/1 and K6.11/2 are observed. Following ground-state depletion of the BR6.11 population, the time-resolved fluroescence intensity monitored at 725 nm increases with two time constants, 12 +/- 3 and approximately 100 ps, both of which correlate well with changes in the picosecond transient absorption data. The resonance Raman spectrum of ground-state BR6.11, measured with low-energy, 560-nm excitation, is significantly different from the spectrum of native BR-570, thus confirming that the

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

    NASA Astrophysics Data System (ADS)

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

    2012-11-01

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

  16. Fluorescent bovine serum albumin interacting with the antitussive quencher dextromethorphan: a spectroscopic insight.

    PubMed

    Durgannavar, Amar K; Patgar, Manjanath B; Nandibewoor, Sharanappa T; Chimatadar, Shivamurti A

    2016-05-01

    The interaction of dextromethorphan hydrobromide (DXM) with bovine serum albumin (BSA) is studied by using fluorescence spectra, UV-vis absorption, synchronous fluorescence spectra (SFS), 3D fluorescence spectra, Fourier transform infrared (FTIR) spectroscopy and circular dichroism under simulated physiological conditions. DXM effectively quenched the intrinsic fluorescence of BSA. Values of the binding constant, K(A), are 7.159 × 10(3), 9.398 × 10(3) and 16.101 × 10(3)  L/mol; the number of binding sites, n, and the corresponding thermodynamic parameters ΔG°, ΔH° and ΔS° between DXM and BSA were calculated at different temperatures. The interaction between DXM and BSA occurs through dynamic quenching and the effect of DXM on the conformation of BSA was analyzed using SFS. The average binding distance, r, between the donor (BSA) and acceptor (DXM) was determined based on Förster's theory. The results of fluorescence spectra, UV-vis absorption spectra and SFS show that the secondary structure of the protein has been changed in the presence of DXM. Copyright © 2015 John Wiley & Sons, Ltd.

  17. High resolution measurements of solar induced chlorophyll fluorescence in the Fraunhofer oxigen bands

    NASA Astrophysics Data System (ADS)

    Mazzoni, M.; Agati, G.; Cecchi, G.; Toci, G.; Mazzinghi, P.

    2017-11-01

    Spectra of solar radiance reflected by leaves close to the Fraunhofer bands show the net contribution of chlorophyll fluorescence emission which adds to the reflected solar spectra. In a laboratory experiment, a low stray light, high resolution, 0.85 m double monochromator was used to filter radiation living leaves still attached to the plant in correspondence of the 687 nm and 760 nm O2 absorption bands. Reference spectra from a non fluorescent white reference were also acquired. Acquisition was performed by a Microchannel plate (MCP) intensified diode array with 512 elements. A fit of the spectral data outside the absorption lines allowed to retrieve the spectral base-line as a function of wavelength for the reference panel and the leaf. Reflectance functions were determined extending the Plascyck equation system to all the resolved lines of the oxygen absorption bands and using the base-lines for the continuum values. Fluorescence was deduced from the same equation system, using both the measured leaf and reference radiance spectra and the leaf reflectance fitting function.

  18. 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)…

  19. 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*.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Bachelor, Paula P.; Jordan, David V.; Harper, Warren W.

    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 measuremore » 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.« less

  1. Temperature-dependent mid-IR absorption spectra of gaseous hydrocarbons

    NASA Astrophysics Data System (ADS)

    Klingbeil, Adam E.; Jeffries, Jay B.; Hanson, Ronald K.

    2007-10-01

    Quantitative mid-IR absorption spectra (2500 3400 cm-1) for 12 pure hydrocarbon compounds are measured at temperatures ranging from 25 to 500 °C using an FTIR spectrometer. The hydrocarbons studied are n-pentane, n-heptane, n-dodecane, 2,2,4-trimethyl-pentane (iso-octane), 2-methyl-butane, 2-methyl-pentane, 2,4,4-trimethyl-1-pentene, 2-methyl-2-butene, propene, toluene, m-xylene, and ethylbenzene. Room-temperature measurements of neat hydrocarbon vapor were made with an instrument resolution of both 0.1 and 1 cm-1 (FWHM) to confirm that the high-resolution setting was required only to resolve the propene absorption spectrum while the spectra of the other hydrocarbons could be resolved with 1 cm-1 resolution. High-resolution (0.1 cm-1), room-temperature measurements of neat hydrocarbons were made at low pressure (˜1 Torr, 133 Pa) and compared to measurements of hydrocarbon/N2 mixtures at atmospheric pressure to verify that no pressure broadening could be observed over this pressure range. The temperature was varied between 25 and 500 °C for atmospheric-pressure measurements of hydrocarbon/N2 mixtures (Xhydrocarbon˜0.06 1.5%) and it was found that the absorption cross section shows simple temperature-dependent behavior for a fixed wavelength over this temperature range. Comparisons with previous FTIR data over a limited temperature range and with high-resolution laser absorption data over a wide temperature range show good agreement.

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

    NASA Astrophysics Data System (ADS)

    Wu, Wenpeng; Cao, Zexing; Zhao, Yi

    2012-03-01

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

  3. 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

  4. Fluorescence spectra of atmospheric aerosol at Adelphi, Maryland, USA: measurement and classification of single particles containing organic carbon

    NASA Astrophysics Data System (ADS)

    Pinnick, Ronald G.; Hill, Steven C.; Pan, Yong-Le; Chang, Richard K.

    We measured laser-induced fluorescence spectra from individual supermicron-sized atmospheric particles drawn into our laboratory at Adelphi, MD, an urban site in the Washington, DC metroplex. A virtural impactor concentrator is used along with an aerodynamic-focusing-nozzle which forms, within an optical chamber, a focused aerosol jet where single aerosol particles can be interrogated on-the-fly with a pulsed 266-nm-wavelength laser. Sample rates are a few liter per minute, and are size dependent. Crossed-diode laser beams indicate when a particle is traversing the sample region and are used to trigger the UV laser to fire and the gated intensified CCD to record the fluorescence spectrum. Our breadboard fluorescence particle spectrometer measures particles in the 3-10 μm diameter size range. Typical trigger rates are a few per second. The usable spectral range is from about 295 to 605 nm. The majority of the particles have very weak fluorescence (on average 8 percent of particles have fluorescence signals above noise). The spectra were grouped using a heirarchical cluster analysis, with parameters chosen so that spectra typically cluster into 4-12 main categories. From the set of all cluster spectra we chose 8 template spectra for reanalyzing all the data. On average, 92 percent (81-94 percent) of the spectra were similar to these templates (using the same thresholds used for the cluster analysis). The major emission bands of the most commonly occurring spectra have peaks: near 460 nm (28 percent of fluorescent particles on average), a very broad hump, and may be humic acids or humic like substances; near 317 nm (on average 24 percent of fluorescent particles); near 321 and 460 nm (a double hump, 12 percent of fluorescent particles); and near 341 nm (8 percent of fluorescent particles). Some of the fluorescence in spectra peaking in the 317-341 nm range is probably from dicyclic aromatics and heterocyclics, including the amino acid tryptophan in biological

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Gambarini, Grazia; Artuso, Emanuele; Liosi, Giulia Maria

    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 themore » apparent threshold dose that was frequently evidenced. (authors)« less

  6. First Principles Optical Absorption Spectra of Organic Molecules Adsorbed on Titania Nanoparticles

    NASA Astrophysics Data System (ADS)

    Baishya, Kopinjol; Ogut, Serdar; Mete, Ersen; Gulseren, Oguz; Ellialtioglu, Sinasi

    2012-02-01

    We present results from first principles computations on passivated rutile TiO2 nanoparticles in both free-standing and dye-sensitized configurations to investigate the size dependence of their optical absorption spectra. The computations are performed using time-dependent density functional theory (TDDFT) as well as GW-Bethe-Salpeter-Equation (GWBSE) methods and compared with each other. We interpret the first principles spectra for free-standing TiO2 nanoparticles within the framework of the classical Mie-Gans theory using the bulk dielectric function of TiO2. We investigate the effects of the titania support on the absorption spectra of a particular set of perylene-diimide (PDI) derived dye molecules, namely brominated PDI (Br2C24H8N2O4) and its glycine and aspartine derivatives.

  7. Excitation of photosystem I by 760 nm femtosecond laser pulses: transient absorption spectra and intermediates

    NASA Astrophysics Data System (ADS)

    Cherepanov, Dmitry A.; Shelaev, Ivan V.; Gostev, Fedor E.; Mamedov, Mahir D.; Petrova, Anastasia A.; Aybush, Arseniy V.; Shuvalov, Vladimir A.; Semenov, Alexey Yu; Nadtochenko, Victor A.

    2017-09-01

    Excitation of photosystem I (PS I) by a femtosecond 760 nm pump leads to one- and two-photon absorption. The one-photon excitation produces intermediates with transient absorption spectra similar to the spectra of the primary [{{{P}}700}+{{{A}}0}-{{A}}1] and secondary [{{{P}}700}+{{A}}0{{{A}}1}-] ion-radical pairs in the PS I reaction center. The two-photon absorption generates the upper level excited states of chlorophyll (Chl) and carotenoid molecules in the antenna. These excited states are converted into the long-lived intermediates and can be tentatively attributed to the excited and charge-transfer ion-radical states of Chl molecules and to the excited states of carotenoids in the antenna. The transient spectra of intermediates generated by two-photon excitation differ from the transient one-photon spectra of the primary and secondary ion-radical pairs.

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

    DTIC Science & Technology

    2013-08-20

    Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/6390--13-9479 Absorption Spectra of Fe, Mn, and Mg Water Complexes Calculated Using ...ABSTRACT c. THIS PAGE 18. NUMBER OF PAGES 17. LIMITATION OF ABSTRACT Absorption Spectra of Fe, Mn, and Mg Water Complexes Calculated Using Density...structure associated with Fe, Mn, and Mg water complexes using time-dependent density functional theory (TD-DFT). Calculation of excited state resonance

  9. Fluorescence of carotenoids. Effect of oxygenation and cis/trans isomerization

    NASA Astrophysics Data System (ADS)

    Jørgensen, Kevin; Stapelfeldt, Henrik; Skibsted, Leif H.

    1992-03-01

    C 40 carotenoids fall, with respect to fluorescence in homogeneous solution, into two distinct groups depending on the presence of a CO group in the molecule. Excitation spectra agree with absorption spectra for the carbonyl derivatives astaxanthin and canthaxanthin. In contrast, zeaxanthin and isomers of β-carotene have a twentyfold increase in fluorescence quantum yield for excitation around 350 nm compared to excitation near the absorption maximum (at approximatively 430 nm). These differences are interpreted in terms of the role of non-emitting 1(n, π*) states related to the CO group in facilitating non-radiative deactivation of higher 1(π, π*) states.

  10. Exciton Absorption Spectra by Linear Response Methods:Application to Conjugated Polymers

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Mosquera, Martin A.; Jackson, Nicholas E.; Fauvell, Thomas J.

    The theoretical description of the timeevolution of excitons requires, as an initial step, the calculation of their spectra, which has been inaccessible to most users due to the high computational scaling of conventional algorithms and accuracy issues caused by common density functionals. Previously (J. Chem. Phys. 2016, 144, 204105), we developed a simple method that resolves these issues. Our scheme is based on a two-step calculation in which a linear-response TDDFT calculation is used to generate orbitals perturbed by the excitonic state, and then a second linear-response TDDFT calculation is used to determine the spectrum of excitations relative to themore » excitonic state. Herein, we apply this theory to study near-infrared absorption spectra of excitons in oligomers of the ubiquitous conjugated polymers poly(3-hexylthiophene) (P3HT), poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV), and poly(benzodithiophene-thieno[3,4-b]thiophene) (PTB7). For P3HT and MEH-PPV oligomers, the calculated intense absorption bands converge at the longest wavelengths for 10 monomer units, and show strong consistency with experimental measurements. The calculations confirm that the exciton spectral features in MEH-PPV overlap with those of the bipolaron formation. In addition, our calculations identify the exciton absorption bands in transient absorption spectra measured by our group for oligomers (1, 2, and 3 units) of PTB7. For all of the cases studied, we report the dominant orbital excitations contributing to the optically active excited state-excited state transitions, and suggest a simple rule to identify absorption peaks at the longest wavelengths. We suggest our methodology could be considered for further evelopments in theoretical transient spectroscopy to include nonadiabatic effects, coherences, and to describe the formation of species such as charge-transfer states and polaron pairs.« less

  11. 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.

  12. Absorption and Fluorescence Properties of Chromophoric Dissolved Organic Matter Produced by Algae.

    PubMed

    Peng, Tong; Lu, Xiao-lan; Su, Rong-guo; Zhang, Dong-mei

    2015-09-01

    Four kinds of diatom (Chaetoceros curvisetus, Phaeodactylum tricornutum, Nitzschia closterium f. minutissima and Navicula halophile) and two kinds of dinoflagellates (Prorocentrum donghaiense and Gymnodinium) were cultured under laboratory conditions. Variations of optical properties of chromophoric dissolved organic matter (CDOM) were studied with absorption and fluorescence excitation-emission matrix spectroscopy(EEM) during growth of marine microalgae in incubation experiment. Absorption spectrum revealed absorption coefficient a(355) (CDOM absorption coefficients at 355 nm) of 6 kinds of marine microalgae above increased by 64.8%, 242.3%, 535.1%, 903.2%, 836% and 196.4%, respectively. Simultaneously, the absorption spectral slope (Sg), determined between 270 and 350 nm, representing the size of molecular weight of CDOM and humic-like composition, decreased by 8.7%, 34.6%, 39.4%, 53.1%, 46.7%, and 35.7%, respectively. Applying parallel factor analysis (PARAFAC) together with EEM got four components of CDOM: C1(Ex/Em=350(260) nm/450 nm), C2 (Ex/Em=260(430) nm/525 nm), C3 (Ex/Em=325 nm/400 nm) and C4(Ex/Em=275 nm/325 nm), which were relative to three humic-like and one protein-like fluorescent components of Nitzschia closterium f. minutissima and Navicula halophile. In incubation experiment, fluorescence intensity of these four components during growth of Nitzschia closterium f. minutissima increased by, respectively, 8.68, 24.9, 7.19 and 39.8 times, and those of Navicula halophile increased by 2.64, 0.07, 4.39 and 12.4 times, respectively. Significant relationships were found between the fluorescence intensity of four components of CDOM, a(355) and Sg. All results demonstrated that both content and molecular weight of CDOM produced by diatom and dinoflagellate studied in incubation experiment increased, but these two parameters changed more obviously of the diatom than those of dinoflagellate; the proportion of humic-like components in the composition of CDOM

  13. Trident: A Universal Tool for Generating Synthetic Absorption Spectra from Astrophysical Simulations

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Hummels, Cameron B.; Smith, Britton D.; Silvia, Devin W.

    Hydrodynamical simulations are increasingly able to accurately model physical systems on stellar, galactic, and cosmological scales; however, the utility of these simulations is often limited by our ability to directly compare them with the data sets produced by observers: spectra, photometry, etc. To address this problem, we have created trident, a Python-based open-source tool for post-processing hydrodynamical simulations to produce synthetic absorption spectra and related data. trident can (i) create absorption-line spectra for any trajectory through a simulated data set mimicking both background quasar and down-the-barrel configurations; (ii) reproduce the spectral characteristics of common instruments like the Cosmic Origins Spectrograph;more » (iii) operate across the ultraviolet, optical, and infrared using customizable absorption-line lists; (iv) trace simulated physical structures directly to spectral features; (v) approximate the presence of ion species absent from the simulation outputs; (vi) generate column density maps for any ion; and (vii) provide support for all major astrophysical hydrodynamical codes. trident was originally developed to aid in the interpretation of observations of the circumgalactic medium and intergalactic medium, but it remains a general tool applicable in other contexts.« less

  14. Trident: A Universal Tool for Generating Synthetic Absorption Spectra from Astrophysical Simulations

    NASA Astrophysics Data System (ADS)

    Hummels, Cameron B.; Smith, Britton D.; Silvia, Devin W.

    2017-09-01

    Hydrodynamical simulations are increasingly able to accurately model physical systems on stellar, galactic, and cosmological scales; however, the utility of these simulations is often limited by our ability to directly compare them with the data sets produced by observers: spectra, photometry, etc. To address this problem, we have created trident, a Python-based open-source tool for post-processing hydrodynamical simulations to produce synthetic absorption spectra and related data. trident can (I) create absorption-line spectra for any trajectory through a simulated data set mimicking both background quasar and down-the-barrel configurations; (II) reproduce the spectral characteristics of common instruments like the Cosmic Origins Spectrograph; (III) operate across the ultraviolet, optical, and infrared using customizable absorption-line lists; (IV) trace simulated physical structures directly to spectral features; (v) approximate the presence of ion species absent from the simulation outputs; (VI) generate column density maps for any ion; and (vii) provide support for all major astrophysical hydrodynamical codes. trident was originally developed to aid in the interpretation of observations of the circumgalactic medium and intergalactic medium, but it remains a general tool applicable in other contexts.

  15. Optical absorption and fluorescence spectroscopy studies of Artepillin C, the major component of green propolis

    NASA Astrophysics Data System (ADS)

    Camuri, Isamara Julia; Costa, Adriano Batista; Ito, Amando Siuiti; Pazin, Wallance Moreira

    2018-06-01

    The bioactivity of propolis against several pathogens is well established, leading to the extensive consumption of that bee product to prevent diseases. Brazilian green propolis, collected by the species Apis mellifera, is one of the most consumed in the world. The chemical composition of green propolis is complex and it has been shown that it displays antioxidant, antimicrobial, anti-inflammatory and antitumor activities, especially due to the high content of Artepillin C. The molecule is a derivative of cinnamic acid with two prenylated groups, responsible for the improvement of the affinity of the compound for lipophilic environment. A carboxylic group (COOH) is also present in the molecule, making it a pH-sensitive compound and the pH-dependent structure of Artepillin C, may modulate its biological activity related to interactions with the cellular membrane of organisms and tissues. Molecular properties of Artepillin C on aqueous solution were examined by optical absorption, steady state and time-resolved fluorescence spectroscopies. Acid-base titration based on the spectral position of the near UV absorption band, resulted in the pKa value of 4.65 for the carboxylic group in Artepillin C. In acidic pH, below the pKa value, an absorption band raised around 350 nm at Artepillin C concentration above 50 μM, due to aggregation of the molecule. In neutral pH, with excitation at 310 nm, Artepillin C presents dual emission at 400 and 450 nm. In pH close to the pKa, the optical spectra show contribution from both protonated and deprotonated species. A three-exponential function was necessary to fit the intensity decays at the different pHs, dominated by a very short lifetime component, around 0.060 ns. The fast decay resulted in emission before fluorescence depolarization, and in values of fluorescence anisotropy higher than could be expected for monomeric forms of the compound. The results give fundamental knowledge about the protonation-deprotonation state of the

  16. Absorption and fluorescence emission spectroscopic characters of naphtho-homologated yy-DNA bases and effect of methanol solution and base pairing.

    PubMed

    Zhang, Laibin; Li, Huifang; Li, Jilai; Chen, Xiaohua; Bu, Yuxiang

    2010-03-01

    A comprehensive theoretical study of electronic transitions of naphtho-homologated base analogs, namely, yy-T, yy-C, yy-A, and yy-G, was performed. The nature of the low-lying excited states is discussed, and the results are compared with those from experiment and also with those of y-bases. Geometrical characteristics of the lowest excited singlet pipi* and npi* states were explored using the CIS method, and the effects of methanol solution and paring with their complementary natural bases on the relevant absorption and emission spectra of these modified bases were examined. The calculated excitation and emission energies agree well with the measured data, where experimental results are available. In methanol solution, the fluorescence from yy-A and yy-G would be expected to occur around 539 and 562 nm, respectively, suggesting that yy-A is a green-colored fluorophore, whereas yy-G is a yellow-colored fluorophore. The methanol solution was found to red-shift both the absorption and emission maxima of yy-A, yy-T, and yy-C, but blue-shift those for yy-G. Generally, though base pairing has no significant effects on the absorption and fluorescence maxima of yy-A, yy-C, and yy-T, it blue-shifts those for yy-G. (c) 2009 Wiley Periodicals, Inc.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    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 LiNi 0.5Mn 1.5O 4, the line shape of the Mn L 3-edge XAS was largely distorted by the self-absorption and saturation effects, while the distortions were less pronounced at the Ni L 3 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 usefulmore » enough for the Ni L edge which is far from the O K edge.« less

  18. Modification of fluorescence and optical properties of Rhodamine B dye doped PVA/Chitosan polymer blend films

    NASA Astrophysics Data System (ADS)

    Padmakumari, R.; Ravindrachary, V.; Mahantesha, B. K.; Sagar, Rohan N.; Sahanakumari, R.; Bhajantri, R. F.

    2018-05-01

    Pure and Rhodamine B doped Poly (vinyl alcohol)/Chitosan composite films are prepared using solution casting method. Fourier transforms infrared spectra (FTIR), Ultraviolet-Visible (UV-Vis), fluorescence studies were used to characterize the prepared polymer films. The FT-IR results show that the appearance of new peaks along with shift in peak positions indicates the interaction of Rhodamine B with PVA-CS blend. Optical absorption edge, band gap and activation energy were determined from UV-Visible studies. The optical absorption edge increases, band gap decreases and activation energy increases with dopant concentration respectively. The corresponding emission spectra were studied using fluorescence spectroscopy. From the fluorescence study the quenching phenomena are observed in emission wavelength range of 607nm-613nm upon excitation with absorption maxima 443nm.

  19. Interventional fluorescence spectroscopy: preliminary results to detect tumor margins during glioma resection with two fluorescence spectra of PpIX

    NASA Astrophysics Data System (ADS)

    Alston, L. M.; Guyotat, J.; Mahieu-Williame, L.; Hebert, M.; Kantapareddy, P.; Meyronet, D.; Rousseau, D.; Montcel, B.

    2017-07-01

    We show the feasibility of using an intraoperative spectroscopic device to identify tumors margins during glioma resection. The collected fluorescence spectra is fitted with two reference spectra of PpIX and the contribution of each spectrum enables to overcome the sensitivity of current techniques by seeing tumor margins and low grade gliomas.

  20. Variable selection based on clustering analysis for improvement of polyphenols prediction in green tea using synchronous fluorescence spectra

    NASA Astrophysics Data System (ADS)

    Shan, Jiajia; Wang, Xue; Zhou, Hao; Han, Shuqing; Riza, Dimas Firmanda Al; Kondo, Naoshi

    2018-04-01

    Synchronous fluorescence spectra, combined with multivariate analysis were used to predict flavonoids content in green tea rapidly and nondestructively. This paper presented a new and efficient spectral intervals selection method called clustering based partial least square (CL-PLS), which selected informative wavelengths by combining clustering concept and partial least square (PLS) methods to improve models’ performance by synchronous fluorescence spectra. The fluorescence spectra of tea samples were obtained and k-means and kohonen-self organizing map clustering algorithms were carried out to cluster full spectra into several clusters, and sub-PLS regression model was developed on each cluster. Finally, CL-PLS models consisting of gradually selected clusters were built. Correlation coefficient (R) was used to evaluate the effect on prediction performance of PLS models. In addition, variable influence on projection partial least square (VIP-PLS), selectivity ratio partial least square (SR-PLS), interval partial least square (iPLS) models and full spectra PLS model were investigated and the results were compared. The results showed that CL-PLS presented the best result for flavonoids prediction using synchronous fluorescence spectra.

  1. Variable selection based on clustering analysis for improvement of polyphenols prediction in green tea using synchronous fluorescence spectra.

    PubMed

    Shan, Jiajia; Wang, Xue; Zhou, Hao; Han, Shuqing; Riza, Dimas Firmanda Al; Kondo, Naoshi

    2018-03-13

    Synchronous fluorescence spectra, combined with multivariate analysis were used to predict flavonoids content in green tea rapidly and nondestructively. This paper presented a new and efficient spectral intervals selection method called clustering based partial least square (CL-PLS), which selected informative wavelengths by combining clustering concept and partial least square (PLS) methods to improve models' performance by synchronous fluorescence spectra. The fluorescence spectra of tea samples were obtained and k-means and kohonen-self organizing map clustering algorithms were carried out to cluster full spectra into several clusters, and sub-PLS regression model was developed on each cluster. Finally, CL-PLS models consisting of gradually selected clusters were built. Correlation coefficient (R) was used to evaluate the effect on prediction performance of PLS models. In addition, variable influence on projection partial least square (VIP-PLS), selectivity ratio partial least square (SR-PLS), interval partial least square (iPLS) models and full spectra PLS model were investigated and the results were compared. The results showed that CL-PLS presented the best result for flavonoids prediction using synchronous fluorescence spectra.

  2. Hierarchy of stochastic Schrödinger equation towards the calculation of absorption and circular dichroism spectra.

    PubMed

    Ke, Yaling; Zhao, Yi

    2017-05-07

    A theoretically solid and numerically exact method is presented for the calculation of absorption and circular dichroism (CD) spectra of molecular aggregates immersed in a harmonic bath constituted as the combination of some prominent quantized vibrational modes and continuous overdamped Brownian oscillators. The feasibility and the validity of newly proposed method are affirmed in the analytical monomer spectra. To go beyond the independent local bath approximation, all the correlations of site energy fluctuations and excitonic coupling fluctuations are included in our strategy, and their influence on the absorption and CD spectra is investigated based on the Frenkel exciton model of homodimer. In the end, a good fit of the absorption and part of CD spectra for the entire B800-B850 ring in the light-harvesting complexes 2 of purple bacteria to the experimental data is given, and the simulation results suggest that the asymmetry in the 800 nm region of CD spectra is actually an indication of B800-B850 inter-ring coupling.

  3. Hierarchy of stochastic Schrödinger equation towards the calculation of absorption and circular dichroism spectra

    NASA Astrophysics Data System (ADS)

    Ke, Yaling; Zhao, Yi

    2017-05-01

    A theoretically solid and numerically exact method is presented for the calculation of absorption and circular dichroism (CD) spectra of molecular aggregates immersed in a harmonic bath constituted as the combination of some prominent quantized vibrational modes and continuous overdamped Brownian oscillators. The feasibility and the validity of newly proposed method are affirmed in the analytical monomer spectra. To go beyond the independent local bath approximation, all the correlations of site energy fluctuations and excitonic coupling fluctuations are included in our strategy, and their influence on the absorption and CD spectra is investigated based on the Frenkel exciton model of homodimer. In the end, a good fit of the absorption and part of CD spectra for the entire B800-B850 ring in the light-harvesting complexes 2 of purple bacteria to the experimental data is given, and the simulation results suggest that the asymmetry in the 800 nm region of CD spectra is actually an indication of B800-B850 inter-ring coupling.

  4. 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.

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

    PubMed

    Chandran, Satheesh; Varma, Ravi

    2016-01-15

    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. Copyright © 2015 Elsevier B.V. All rights reserved.

  6. Concentration Dependence of Gold Nanoparticles for Fluorescence Enhancement

    NASA Astrophysics Data System (ADS)

    Solomon, Joel; Wittmershaus, Bruce

    Noble metal nanoparticles possess a unique property known as surface plasmon resonance in which the conduction electrons oscillate due to incoming light, dramatically increasing their absorption and scattering of light. The oscillating electrons create a varying electric field that can affect nearby molecules. The fluorescence and photostability of fluorophores can be enhanced significantly when they are near plasmonic nanoparticles. This effect is called metal enhanced fluorescence (MEF). MEF from two fluorescence organic dyes, Lucifer Yellow CH and Riboflavin, was measured with different concentrations of 50-nm colloidal gold nanoparticles (Au-NP). The concentration range of Au-NP was varied from 2.5 to 250 pM. To maximize the interaction, the dyes were chosen so their emission spectra had considerable overlap with the absorption spectra of the Au-NP, which is common in MEF studies. If the dye molecules are too close to the surface of Au-NP, fluorescence quenching can occur instead of MEF. To try to observe this difference, silica-coated Au-NP were compared to citrate-based Au-NP; however, fluorescence quenching was observed with both Au-NP. This material is based upon work supported by the National Science Foundation under Grant Number NSF-ECCS-1306157.

  7. 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.

  8. Photoluminescence and gain/absorption spectra of a driven-dissipative electron-hole-photon condensate

    NASA Astrophysics Data System (ADS)

    Hanai, Ryo; Littlewood, Peter B.; Ohashi, Yoji

    2018-06-01

    We investigate theoretically nonequilibrium effects on photoluminescence and gain/absorption spectra of a driven-dissipative exciton-polariton condensate, by employing the combined Hartree-Fock-Bogoliubov theory with the generalized random phase approximation extended to the Keldysh formalism. Our calculated photoluminescence spectra is in semiquantitative agreement with experiments, where features such as a blue shift of the emission from the condensate, the appearance of the dispersionless feature of a diffusive Goldstone mode, and the suppression of the dispersive profile of the mode are obtained. We show that the nonequilibrium nature of the exciton-polariton condensate strongly suppresses the visibility of the Bogoliubov dispersion in the negative energy branch (ghost branch) in photoluminescence spectra. We also show that the trace of this branch can be captured as a hole burning effect in gain/absorption spectra. Our results indicate that the nonequilibrium nature of the exciton-polariton condensate strongly reduces quantum depletion, while a scattering channel to the ghost branch is still present.

  9. 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. Copyright © 2014 Elsevier B.V. All rights reserved.

  10. Mathematical modeling of reflectance and intrinsic fluorescence for cancer detection in human pancreatic tissue

    NASA Astrophysics Data System (ADS)

    Wilson, Robert H.; Chandra, Malavika; Scheiman, James; Simeone, Diane; McKenna, Barbara; Purdy, Julianne; Mycek, Mary-Ann

    2009-02-01

    Pancreatic adenocarcinoma has a five-year survival rate of only 4%, largely because an effective procedure for early detection has not been developed. In this study, mathematical modeling of reflectance and fluorescence spectra was utilized to quantitatively characterize differences between normal pancreatic tissue, pancreatitis, and pancreatic adenocarcinoma. Initial attempts at separating the spectra of different tissue types involved dividing fluorescence by reflectance, and removing absorption artifacts by applying a "reverse Beer-Lambert factor" when the absorption coefficient was modeled as a linear combination of the extinction coefficients of oxy- and deoxy-hemoglobin. These procedures demonstrated the need for a more complete mathematical model to quantitatively describe fluorescence and reflectance for minimally-invasive fiber-based optical diagnostics in the pancreas.

  11. 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

  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. 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…

  14. Fluorescence and picosecond induced absorption from the lowest singlet excited states of quercetin in solutions and polymer films

    NASA Astrophysics Data System (ADS)

    Bondarev, S. L.; Tikhomirov, S. A.; Buganov, O. V.; Knyukshto, V. N.; Raichenok, T. F.

    2017-03-01

    The spectroscopic and photophysical properties of the biologically important plant antioxidant quercetin in organic solvents, polymer films of polyvinyl alcohol, and a buffer solution at pH 7.0 are studied by stationary luminescence and femtosecond laser spectroscopy at room temperature and 77 K. The large magnitude of the dipole moment of the quercetin molecule in the excited Franck-Condon state μ e FC = 52.8 C m indicates the dipolar nature of quercetin in this excited state. The transient induced absorption spectra S 1→ S n in all solvents are characterized by a short-wave band at λ abs max = 460 nm with exponential decay times in the range of 10.0-20.0 ps. In the entire spectral range at times of >100 ps, no residual induced absorption was observed that could be attributed to the triplet-triplet transitions T 1 → T k in quercetin. In polar solvents, two-band fluorescence was also recorded at room temperature, which is due to the luminescence of the initial enol form of quercetin ( 415 nm) and its keto form with a transferred proton (550 nm). The short-wave band is absent in nonpolar 2-methyltetrahydrofuran (2-MTHF). The spectra of fluorescence and fluorescence excitation exhibit a low dependence on the wavelength of excitation and detection, which may be related to the solvation and conformational changes in the quercetin molecule. Decreasing the temperature of a glassy-like freezing quercetin solution in ethanol and 2-MTHF to 77 K leads to a strong increase in the intensity (by a factor of 100) of both bands. The energy circuits for the proton transfer process are proposed depending on the polarity of the medium. The main channel for the exchange of electronic excitation energy in the quercetin molecule at room temperature is the internal conversion S 1 ⇝ S 0, induced by the state with a proton transfer.

  15. The temporal evolution process from fluorescence bleaching to clean Raman spectra of single solid particles optically trapped in air

    NASA Astrophysics Data System (ADS)

    Gong, Zhiyong; Pan, Yong-Le; Videen, Gorden; Wang, Chuji

    2017-12-01

    We observe the entire temporal evolution process of fluorescence and Raman spectra of single solid particles optically trapped in air. The spectra initially contain strong fluorescence with weak Raman peaks, then the fluorescence was bleached within seconds, and finally only the clean Raman peaks remain. We construct an optical trap using two counter-propagating hollow beams, which is able to stably trap both absorbing and non-absorbing particles in air, for observing such temporal processes. This technique offers a new method to study dynamic changes in the fluorescence and Raman spectra from a single optically trapped particle in air.

  16. Theoretical investigation on ratiometric two-photon fluorescent probe for Zn2+ detection based on ICT mechanism

    NASA Astrophysics Data System (ADS)

    Huang, Shuang; Yang, Bao-Zhu; Ren, Ai-Min

    2016-06-01

    OPA (one-photon absorption), TPA (two-photon absorption) and fluorescence properties of a free ligand L upon coordination with Zn2+, and the regeneration with CN- were investigated in theory. According to our research, OPA spectra of ligand L show red-shift binding with Zn2+ while blue-shift with CN-. The fluorescence spectra and TPA wavelength are shifted in the same situation as those of OPA spectra. The value of TPA cross-section decreased at first, and then increased to 1813 GM for [L-Zn(CN)4]2-. Intramolecular charge transfer (ICT) mechanism was investigated by natural bond orbital (NBO) analysis. It demonstrates that L is hopeful to be a good ratiometric fluorescent probe for zinc ion detection in solution, and it can regenerate after CN- was introduced.

  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. 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

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lewandowski, Wojciech; Rożko, Karolina; Kijak, Jarosław

    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 putmore » 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.« less

  20. Deletion mapping of the Aequorea victoria green fluorescent protein.

    PubMed

    Dopf, J; Horiagon, T M

    1996-01-01

    Aequorea victoria green fluorescent protein (GFP) is a promising fluorescent marker which is active in a diverse array of prokaryotic and eukaryotic organisms. A key feature underlying the versatility of GFP is its capacity to undergo heterocyclic chromophore formation by cyclization of a tripeptide present in its primary sequence and thereby acquiring fluorescent activity in a variety of intracellular environments. In order to define further the primary structure requirements for chromophore formation and fluorescence in GFP, a series of N- and C-terminal GFP deletion variant expression vectors were created using the polymerase chain reaction. Scanning spectrofluorometric analyses of crude soluble protein extracts derived from eleven GFP expression constructs revealed that amino acid (aa) residues 2-232, of a total of 238 aa in the native protein, were required for the characteristic emission and absorption spectra of native GFP. Heterocyclic chromophore formation was assayed by comparing the absorption spectrum of GFP deletion variants over the 300-500-nm range to the absorption spectra of full-length GFP and GFP deletion variants missing the chromophore substrate domain from the primary sequence. GFP deletion variants lacking fluorescent activity showed no evidence of heterocyclic ring structure formation when the soluble extracts of their bacterial expression hosts were studied at pH 7.9. These observations suggest that the primary structure requirements for the fluorescent activity of GFP are relatively extensive and are compatible with the view that much of the primary structure serves an autocatalytic function.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

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

    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.

  2. 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.

  3. Ionic species produced on gamma radiolysis: Studies by matrix isolation technique—I. Electronic absorption spectra of perfluorosubstituted aromatic radical anions

    NASA Astrophysics Data System (ADS)

    Shou-te, Lian C. T.; Mittal, Jai P.

    The absorption spectra of several perfluorosubstituted aromatic radical anions are compared with the corresponding perhydro compounds in which the various transitions involved have been assigned to those predicted theoretically. The electronic absorption spectra were obtained for pentafluorostyrene, pentafluorobenzaldehyde, pentafluorobenzoic acid, pentafluorobenzonitride, tetrafluorophthalic acid and pentafluoroaniline, by gamma radiolysis in 2-methyltetrahydrofuran at 77 K. A general similarity in the absorption spectra between the perfluorinated and the corresponding perhydro radical anion is observed except for a shift in the absorption band.

  4. 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.

  5. 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.

  6. 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.

  7. Quantitative X-ray fluorescence computed tomography for low-Z samples using an iterative absorption correction algorithm

    NASA Astrophysics Data System (ADS)

    Huang, Rong; Limburg, Karin; Rohtla, Mehis

    2017-05-01

    X-ray fluorescence computed tomography is often used to measure trace element distributions within low-Z samples, using algorithms capable of X-ray absorption correction when sample self-absorption is not negligible. Its reconstruction is more complicated compared to transmission tomography, and therefore not widely used. We describe in this paper a very practical iterative method that uses widely available transmission tomography reconstruction software for fluorescence tomography. With this method, sample self-absorption can be corrected not only for the absorption within the measured layer but also for the absorption by material beyond that layer. By combining tomography with analysis for scanning X-ray fluorescence microscopy, absolute concentrations of trace elements can be obtained. By using widely shared software, we not only minimized the coding, took advantage of computing efficiency of fast Fourier transform in transmission tomography software, but also thereby accessed well-developed data processing tools coming with well-known and reliable software packages. The convergence of the iterations was also carefully studied for fluorescence of different attenuation lengths. As an example, fish eye lenses could provide valuable information about fish life-history and endured environmental conditions. Given the lens's spherical shape and sometimes the short distance from sample to detector for detecting low concentration trace elements, its tomography data are affected by absorption related to material beyond the measured layer but can be reconstructed well with our method. Fish eye lens tomography results are compared with sliced lens 2D fluorescence mapping with good agreement, and with tomography providing better spatial resolution.

  8. 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.

  9. Dependence of the electronic absorption spectra of aqueous solutions of iodine monochloride on the conditions of dilution and storage time

    NASA Astrophysics Data System (ADS)

    Klyubin, V. V.; Klyubina, K. A.; Makovetskaya, K. N.

    2017-04-01

    The electronic absorption spectra of aqueous solutions of iodine monochloride ICl are studied. The spectra of as-prepared solutions display the absorption band associated with hydrated ICl molecules. An additional band indicating that molecular iodine was formed in the solution emerges in the spectrum as dissolution takes place. Only the band belonging to iodine monochloride remains in the absorption spectra, and no additional bands appear after chloride anions Cl- are added to the solution. The absorption spectrum becomes more complex when ICl is dissolved in an alkaline medium. The band belonging to molecular iodine emerges in the spectra at low alkali concentrations, while being transformed to other shorter-wavelength bands at high alkali concentrations (pH ≥ 12).

  10. Temperature dependence of Ti:Sapphire fluorescence spectra for the design of cryogenic cooled Ti:Sapphire CPA laser.

    PubMed

    Burton, Harry; Debardelaben, Christopher; Amir, Wafa; Planchon, Thomas A

    2017-03-20

    The fluorescence spectra of titanium doped sapphire (Ti:Sapphire) crystals were measured for temperature ranging from 300K to 77K. The resulting gain cross-section line shapes were calculated and used in a three-dimensional amplification model to illustrate the importance of the precise knowledge of these fluorescence spectra for the design of cryogenic cooled Ti:Sapphire based chirped-pulse laser amplifiers.

  11. [Study of the Detecting System of CH4 and SO2 Based on Spectral Absorption Method and UV Fluorescence Method].

    PubMed

    Wang, Shu-tao; Wang, Zhi-fang; Liu, Ming-hua; Wei, Meng; Chen, Dong-ying; Wang, Xing-long

    2016-01-01

    According to the spectral absorption characteristics of polluting gases and fluorescence characteristics, a time-division multiplexing detection system is designed. Through this system we can detect Methane (CH4) and sulfur dioxide (SO2) by using spectral absorption method and the SO2 can be detected by using UV fluorescence method. The system consists of four parts: a combination of a light source which could be switched, the common optical path, the air chamber and the signal processing section. The spectral absorption characteristics and fluorescence characteristics are measured first. Then the experiment of detecting CH4 and SO2 through spectral absorption method and the experiment of detecting SO2 through UV fluorescence method are conducted, respectively. Through measuring characteristics of spectral absorption and fluorescence, we get excitation wavelengths of SO2 and CH4 measured by spectral absorption method at the absorption peak are 280 nm and 1.64 μm, respectively, and the optimal excitation wavelength of SO2 measured by UV fluorescence method is 220 nm. we acquire the linear relation between the concentration of CH4 and relative intensity and the linear relation between the concentration of SO2 and output voltage after conducting the experiment of spectral absorption method, and the linearity are 98.7%, 99.2% respectively. Through the experiment of UV fluorescence method we acquire that the relation between the concentration of SO2 and the voltage is linear, and the linearity is 99.5%. Research shows that the system is able to be applied to detect the polluted gas by absorption spectrum method and UV fluorescence method. Combing these two measurement methods decreases the costing and the volume, and this system can also be used to measure the other gases. Such system has a certain value of application.

  12. Exploration of faint absorption bands in the reflectance spectra of the asteroids by method of optimal smoothing: Vestoids

    NASA Astrophysics Data System (ADS)

    Shestopalov, D. I.; McFadden, L. A.; Golubeva, L. F.

    2007-04-01

    An optimization method of smoothing noisy spectra was developed to investigate faint absorption bands in the visual spectral region of reflectance spectra of asteroids and the compositional information derived from their analysis. The smoothing algorithm is called "optimal" because the algorithm determines the best running box size to separate weak absorption bands from the noise. The method is tested for its sensitivity to identifying false features in the smoothed spectrum, and its correctness of forecasting real absorption bands was tested with artificial spectra simulating asteroid reflectance spectra. After validating the method we optimally smoothed 22 vestoid spectra from SMASS1 [Xu, Sh., Binzel, R.P., Burbine, T.H., Bus, S.J., 1995. Icarus 115, 1-35]. We show that the resulting bands are not telluric features. Interpretation of the absorption bands in the asteroid spectra was based on the spectral properties of both terrestrial and meteorite pyroxenes. The bands located near 480, 505, 530, and 550 nm we assigned to spin-forbidden crystal field bands of ferrous iron, whereas the bands near 570, 600, and 650 nm are attributed to the crystal field bands of trivalent chromium and/or ferric iron in low-calcium pyroxenes on the asteroids' surface. While not measured by microprobe analysis, Fe 3+ site occupancy can be measured with Mössbauer spectroscopy, and is seen in trace amounts in pyroxenes. We believe that trace amounts of Fe 3+ on vestoid surfaces may be due to oxidation from impacts by icy bodies. If that is the case, they should be ubiquitous in the asteroid belt wherever pyroxene absorptions are found. Pyroxene composition of four asteroids of our set is determined from the band position of absorptions at 505 and 1000 nm, implying that there can be orthopyroxenes in all range of ferruginosity on the vestoid surfaces. For the present we cannot unambiguously interpret of the faint absorption bands that are seen in the spectra of 4005 Dyagilev, 4038

  13. 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.

  14. Aprotic solvents effect on the UV-visible absorption spectra of bixin

    NASA Astrophysics Data System (ADS)

    Rahmalia, Winda; Fabre, Jean-François; Usman, Thamrin; Mouloungui, Zéphirin

    2014-10-01

    We describe here the effects of aprotic solvents on the spectroscopic characteristics of bixin. Bixin was dissolved in dimethyl sulfoxide, acetone, dichloromethane, ethyl acetate, chloroform, dimethyl carbonate, cyclohexane and hexane, separately, and its spectra in the resulting solutions were determined by UV-visible spectrophotometry at normal pressure and room temperature. We analyzed the effect of aprotic solvents on λmax according to Onsager cavity model and Hansen theory, and determined the approximate absorption coefficient with the Beer-Lambert law. We found that the UV-visible absorption spectra of bixin were found to be solvent dependent. The S0 → S2 transition energy of bixin in solution was dependent principally on the refractive index of the solvents and the bixin-solvent dispersion interaction. There was a small influence of the solvents dielectric constant, permanent dipole interaction and hydrogen bonding occurred between bixin and solvents. The absorbance of bixin in various solvents, with the exception of hexane, increased linearly with concentration.

  15. Laser induced fluorescence in algae: A new technique for remote detection

    NASA Technical Reports Server (NTRS)

    Friedman, E. J.; Hickman, G. D.

    1972-01-01

    Measurements of the absorption and fluorescence spectra were obtained for four various types of marine and fresh water algae using a pulsed N2/Ne dye laser as the source of excitation. The absorption maxima for the algae ranged from 420 to 675 nm, while their fluorescent spectra ranged from 580 to 685 nm. It appears feasible that various algal species can be identified by detection of their fluorescent signatures using a tunable laser as the excitation source. However, if one is concerned only with detection of chlorophyll a, the optimum excitation is approximately 600 + 50 nm while detection is at 685 nm. An analysis of both calculations and laboratory results indicates that it should be feasible to measure chlorophyll a in concentrations as low as 1.0 mg/m3 using a 100 kW peak pulsed laser from an altitude of 500 meters.

  16. 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.

  17. 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

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

    DTIC Science & Technology

    2016-06-03

    Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/6390--16-9681 Calculation of Vibrational and Electronic Excited-State Absorption Spectra...NUMBER OF PAGES 17. LIMITATION OF ABSTRACT Calculation of Vibrational and Electronic Excited-State Absorption Spectra of Arsenic-Water Complexes Using...Unclassified Unlimited Unclassified Unlimited 59 Samuel G. Lambrakos (202) 767-2601 Calculations are presented of vibrational and electronic excited-state

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Bartnik, A.; Wachulak, P.; Fiedorowicz, H.

    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 EUVmore » 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.« less

  20. [Laser Induced Fluorescence Spectroscopic Analysis of Aromatics from One Ring to Four Rings].

    PubMed

    Zhang, Peng; Liu, Hai-feng; Yue, Zong-yu; Chen, Bei-ling; Yao, Ming-fa

    2015-06-01

    In order to distinguish small aromatics preferably, a Nd : YAG Laser was used to supply an excitation laser, which was adjusted to 0.085 J x cm(-2) at 266 nm. Benzene, toluene, naphthalene, phenanthrene, anthracene, pyrene and chrysene were used as the representative of different rings aromatics. The fluorescence emission spectra were researched for each aromatic hydrocarbon and mixtures by Laser induced fluorescence (LIF). Results showed that the rings number determined the fluorescence emission spectra, and the structure with same rings number did not affect the emission fluorescence spectrum ranges. This was due to the fact that the absorption efficiency difference at 266 nm resulted in that the fluorescence intensities of each aromatic hydrocarbon with same rings number were different and the fluorescence intensities difference were more apparently with aromatic ring number increasing. When the absorption efficiency was similar at 266 nm and the concentrations of each aromatic hydrocarbon were same, the fluorescence intensities were increased with aromatic ring number increasing. With aromatic ring number increasing, the fluorescence spectrum and emission peak wavelength were all red-shifted from ultraviolet to visible and the fluorescence spectrum range was also wider as the absorption efficiency was similar. The fluorescence emission spectra from one to four rings could be discriminated in the following wavelengths, 275 to 320 nm, 320 to 375 nm, 375 to 425 nm, 425 to 556 nm, respectively. It can be used for distinguish the type of the polycyclic aromatic hydrocarbons (PAHs) as it exists in single type. As PAHs are usually exist in a variety of different rings number at the same time, the results for each aromatic hydrocarbon may not apply to the aromatic hydrocarbon mixtures. For the aromatic hydrocarbon mixtures, results showed that the one- or two-ring PAHs in mixtures could not be detected by fluorescence as three- or four-ring PAHs existed in mixture

  1. Single crystal absorption spectra of synthetic Ti, Fe-substituted pyropes

    NASA Astrophysics Data System (ADS)

    Khomenko, V. M.; Langer, K.; Andrut, M.; Koch-Müller, M.; Vishnevsky, A. A.

    1994-11-01

    Synthetic pyrope crystals up to 0.5 mm in diameter, substituted by titanium or by titanium plus iron, were grown under defined conditions of P, T, f_{O_2 } in the presence of water using a piston-cylinder device. The crystals were characterized by X-ray and microprobe techniques. Their single-crystal optical absorption spectra were measured by means of a microscope-spectrometer. Two absorption bands at 16100 and 22300 cm{cm-1} in the spectra of pale-blue Fe-free Ti-bearing pyropes, grown under reduced conditions, were identified as originating from spin-allowed transitions, derived from 2 T 2g → 2 E g of octahedral Ti3+ ions. The splitting value of the excited 2E g state, 6200 cm-1, and the crystal field parameter of Ti3+ in pyrope Δ 0 = 19 200 cm-1 are both in agreement with literature data. In spectra of brown Fe, Ti-bearing garnets, a broad band at 23000 cm-1 was interpreted as a Fe2+[8] → Ti4+[6] charge-transfer band. The spectral position and width of this band agree with those observed for a FeTi charge transfer band in natural garnets. Fe, Ti-containing garnets synthesized at relatively high oxygen fugacity (10-11,0 atm), which permits a fraction of Fe3+ to enter the garnet, show an additional Fe2+[8] → Fe3+[6] charge transfer band at 19800 cm-1.

  2. 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. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. 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.

  4. Structural characterization of astaxanthin aggregates as revealed by analysis and simulation of optical spectra

    NASA Astrophysics Data System (ADS)

    Lu, Liping; Hu, Taoping; Xu, Zhigang

    2017-10-01

    Carotenoids can self-assemble in hydrated polar solvents to form J- or H-type aggregates, inducing dramatic changes in photophysical properties. Here, we measured absorption and emission spectra of astaxanthin in ethanol-water solution using ultraviolet-visible and fluorescence spectrometers. Two types of aggregates were distinguished in mixed solution at different water contents by absorption spectra. After addition of water, all probed samples immediately formed H-aggregates with maximum blue shift of 31 nm. In addition, J-aggregate was formed in 1:3 ethanol-water solution measured after an hour. Based on Frenkel exciton model, we calculated linear absorption and emission spectra of these aggregates to describe aggregate structures in solution. For astaxanthin, experimental results agreed well with the fitted spectra of H-aggregate models, which consisted of tightly packed stacks of individual molecules, including hexamers, trimers, and dimers. Transition moment of single astaxanthin in ethanol was obtained by Gaussian 09 program package to estimate the distance between molecules in aggregates. Intermolecular distance of astaxanthin aggregates ranges from 0.45 nm to 0.9 nm. Fluorescence analysis showed that between subbands, strong exciton coupling induced rapid relaxation of H-aggregates. This coupling generated larger Stokes shift than monomers and J-aggregates.

  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. Seasonal variability in CDOM absorption and fluorescence properties in the Barataria Basin, Louisiana, USA.

    PubMed

    Singh, Shatrughan; D'Sa, Eurico; Swenson, Erick

    2010-01-01

    Absorption and fluorescence properties of chromophoric dissolved organic matter (CDOM) along a 124 km transect in the Barataria Basin, a large estuary located in Louisiana, USA, were investigated during high and low flow periods of the Mississippi River in the spring and winter of 2008-2009. Mean CDOM absorption at 355 nm from the marine to the freshwater end member stations ranged from (3.25 +/- 0.56) to (20.76 +/- 2.43) m(-1) for the three month high flow period whereas it varied from (1.48 +/- 1.08) to (25.45 +/- 7.03) m(-1) for the same stations during low flow period. Corresponding salinity values at these stations indicated the influence of river and shelf exchanges in the lower basin and precipitation and runoff in the upper basin. An inverse relationship of CDOM absorbance and fluorescence with salinity observed in the basin could be a useful indicator of salinity. CDOM fluorescence also varied over a large range showing an approximately 8 to 12-fold increase between the marine and freshwater end members for the two flow seasons. Excitation-emission matrix spectral plots indicated the presence of various fluorescence components with highest being the A-peak, lowest the T-peak, and the C and M-peaks showing similar trends along the transect. During low flow season the A/C ratio were well correlated with station locations indicating increased terrestrial influence towards the upper basin. CDOM absorption and fluorescence at 355 nm were highly correlated and independent of CDOM sources suggesting that fluorescence could be used to characterize CDOM in the basin.

  7. Substituent and Solvent Effects on the Absorption Spectra of Cation-π Complexes of Benzene and Borazine: A Theoretical Study.

    PubMed

    Sarmah, Nabajit; Bhattacharyya, Pradip Kr; Bania, Kusum K

    2014-05-29

    Time-dependent density functional theory (TDDFT) has been used to predict the absorption spectra of cation-π complexes of benzene and borazine. Both polarized continuum model (PCM) and discrete solvation model (DSM) and a combined effect of PCM and DSM on the absorption spectra have been elucidated. With decrease in size of the cation, the π → π* transitions of benzene and borazine are found to undergo blue and red shift, respectively. A number of different substituents (both electron-withdrawing and electron-donating) and a range of solvents (nonpolar to polar) have been considered to understand the effect of substituent and solvents on the absorption spectra of the cation-π complexes of benzene and borazine. Red shift in the absorption spectra of benzene cation-π complexes are observed with both electron-donating groups (EDGs) and electron-withdrawing groups (EWGs). The same trend has not been observed in the case of substituted borazine cation-π complexes. The wavelength of the electronic transitions corresponding to cation-π complexes correlates well with the Hammet constants (σ p and σ m ). This correlation indicates that the shifting of spectral lines of the cation-π complexes on substitution is due to both resonance and inductive effect. On incorporation of solvent phases, significant red or blue shifting in the absorption spectra of the complexes has been observed. Kamlet-Taft multiparametric equation has been used to explain the effect of solvent on the absorption spectra of complexes. Polarity and polarizability are observed to play an important role in the solvatochromism of the cation-π complexes.

  8. High resolution x-ray fluorescence spectroscopy - a new technique for site- and spin-selectivity

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Wang, Xin

    1996-12-01

    X-ray spectroscopy has long been used to elucidate electronic and structural information of molecules. One of the weaknesses of x-ray absorption is its sensitivity to all of the atoms of a particular element in a sample. Through out this thesis, a new technique for enhancing the site- and spin-selectivity of the x-ray absorption has been developed. By high resolution fluorescence detection, the chemical sensitivity of K emission spectra can be used to identify oxidation and spin states; it can also be used to facilitate site-selective X-ray Absorption Near Edge Structure (XANES) and site-selective Extended X-ray Absorption Fine Structure (EXAFS). Themore » spin polarization in K fluorescence could be used to generate spin selective XANES or spin-polarized EXAFS, which provides a new measure of the spin density, or the nature of magnetic neighboring atoms. Finally, dramatic line-sharpening effects by the combination of absorption and emission processes allow observation of structure that is normally unobservable. All these unique characters can enormously simplify a complex x-ray spectrum. Applications of this novel technique have generated information from various transition-metal model compounds to metalloproteins. The absorption and emission spectra by high resolution fluorescence detection are interdependent. The ligand field multiplet model has been used for the analysis of K{alpha} and K{beta} emission spectra. First demonstration on different chemical states of Fe compounds has shown the applicability of site selectivity and spin polarization. Different interatomic distances of the same element in different chemical forms have been detected using site-selective EXAFS.« less

  9. Laboratory absorption spectra of molecules at interstellar cloud temperatures - First measurements on CO at about 97 nm

    NASA Technical Reports Server (NTRS)

    Smith, P. L.; Yoshino, K.; Stark, G.; Ito, K.; Stevens, M. H.

    1991-01-01

    In the 91-100 nm spectral region, where absorption of photons by interstellar CO usually leads to dissociation, laboratory spectra obtained at 295 K show that most CO bands are both overlapped and perturbed. Reliable band oscillator strengths cannot be extracted from such spectra. As a consequence, synthetic extreme-ultraviolet absorption spectra for CO at the low temperatures that prevail in interstellar clouds are uncertain. A supersonic expansion technique has been used to cool CO to 30 K and three bands in the 97-nm region have been studied with high spectral resolution. The measured spectrum at 30 K is in reasonable agreement with some published modeled spectra, but the ratios of integrated cross sections are somewhat different from those determined from low resolution spectra obtained at 295 K, in which the bands are blended.

  10. Solvatochromic fluorescence characteristics of cinnamoyl pyrone derivatives

    NASA Astrophysics Data System (ADS)

    Benosmane, Nadjib; Boutemeur, Baya; Hamdi, Safouane M.; Hamdi, Maamar; Silva, Artur S. M.

    2017-12-01

    The solvatochromic fluorescence behavior of cinnamoyl pyrone derivatives has been studied in several polar and non-polar solvents. The fluorescence spectra of these compounds exhibit red shift from its absorption spectra and present an excellent correlation with solvent polarity. Cinnamoyl pyrones show a significant spectral shift in fluorescence emission as a function of water composition in binary aqueous solutions mixture. This change is due to the specific intermolecular hydrogen bonding of cinnamoyl pyrones with a molecules of water, due to the deactivation of the lowest excited singlet state of these compounds. The relative quantum yields are calculated. It is found that the quantum yields of the cinnamoyl pyrones vary with the change in the solvent polarity indicating the dependency of fluorescence properties on the solvent nature. It has been observed that the addition of water and pH medium can affect the fluorescence properties of cinnamoyl pyrones in ethanol. This study exhibited that due to the solvent sensitive emission, cinnamoyl pyrone derivatives are a good compound to be used as fluorescence probes.

  11. X-ray absorption spectra: Graphene, h-BN, and their alloy

    NASA Astrophysics Data System (ADS)

    Bhowmick, Somnath; Rusz, Jan; Eriksson, Olle

    2013-04-01

    Using first-principles density functional theory calculations, in conjunction with the Mahan-Nozières-de Dominicis theory, we calculate the x-ray absorption spectra of the alloys of graphene and monolayer hexagonal boron nitride on a Ni (111) substrate. The chemical neighborhood of the constituent atoms (B, C, and N) inside the alloy differs from that of the parent phases. In a systematic way, we capture the change in the K-edge spectral shape, depending on the chemical neighborhood of B, C, and N. Our work also reiterates the importance of the dynamical core-hole screening for a proper description of the x-ray absorption process in sp2-bonded layered materials.

  12. Fluorescence spectra of Cr3+ dimers in LiNbO3

    NASA Astrophysics Data System (ADS)

    Jia, Weiyi; Liu, Huimin; Knutson, R.; Yen, W. M.

    1990-06-01

    Fine spectral structure has been observed in both fluorescence and excitation spectra of Cr3+:LiNbO3 on the high-energy side of the broadband emission from 4T2 at 10 K. The lifetimes of the structures are found to be much longer than the lifetime of the broadband 4T2 fluorescence. These sharp lines are assigned to the 2E-->4A2 emissions (R lines) from two types of Cr3+ sites arising from charge compensation; Cr3+ ions are found to substitute both for Li+ and for Nb5+ sites and to form dimerlike pairs.

  13. 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

  14. 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

  15. Excitation Spectra and Brightness Optimization of Two-Photon Excited Probes

    PubMed Central

    Mütze, Jörg; Iyer, Vijay; Macklin, John J.; Colonell, Jennifer; Karsh, Bill; Petrášek, Zdeněk; Schwille, Petra; Looger, Loren L.; Lavis, Luke D.; Harris, Timothy D.

    2012-01-01

    Two-photon probe excitation data are commonly presented as absorption cross section or molecular brightness (the detected fluorescence rate per molecule). We report two-photon molecular brightness spectra for a diverse set of organic and genetically encoded probes with an automated spectroscopic system based on fluorescence correlation spectroscopy. The two-photon action cross section can be extracted from molecular brightness measurements at low excitation intensities, while peak molecular brightness (the maximum molecular brightness with increasing excitation intensity) is measured at higher intensities at which probe photophysical effects become significant. The spectral shape of these two parameters was similar across all dye families tested. Peak molecular brightness spectra, which can be obtained rapidly and with reduced experimental complexity, can thus serve as a first-order approximation to cross-section spectra in determining optimal wavelengths for two-photon excitation, while providing additional information pertaining to probe photostability. The data shown should assist in probe choice and experimental design for multiphoton microscopy studies. Further, we show that, by the addition of a passive pulse splitter, nonlinear bleaching can be reduced—resulting in an enhancement of the fluorescence signal in fluorescence correlation spectroscopy by a factor of two. This increase in fluorescence signal, together with the observed resemblance of action cross section and peak brightness spectra, suggests higher-order photobleaching pathways for two-photon excitation. PMID:22385865

  16. Universal formulation of excitonic linear absorption spectra in all semiconductor microstructures

    NASA Astrophysics Data System (ADS)

    Lefebvre, Pierre; Christol, Philippe; Mathieu, Henry

    1995-01-01

    We present a generalization of the well-known exciton absorption calculations of Elliott [Phys. Rev. 108, 1384 (1957)], in the 3-dimensional case, and of Shinada and Sugano [J. Phys. Soc. Japan 21, 1936 (1966)], for 2-dimensional media: We calculate the optical absorption spectra of bound and unbound exciton states, by using a metric space with a noninteger dimension α (1 < α), obtaining almost exactly the same theoretical lineshapes as those resulting from accurate but costly numerical approaches [Chuang et al. Phys. Rev. B, 43, 1500 (1991); Benner and Haug, Phys. Rev. B 47, 15750 (1993)].

  17. Laser Induced Fluorescence Spectroscopy of Neutral and Ionized Polycyclic Aromatic Hydrocarbons in the Cosmic Simulation Chamber

    NASA Technical Reports Server (NTRS)

    Bejaoui, Salma; Salama, Farid; Contreras, Cesar; Sciamma O'Brien, Ella; Foing, Bernard; Pascale, Ehrenfreund

    2015-01-01

    Polycyclic aromatic hydrocarbon (PAH) molecules are considered the best carriers to account for the ubiquitous infrared emission bands. PAHs have also been proposed as candidates to explain the diffuse interstellar bands (DIBs), a series of absorption features seen on the interstellar extinction curve and are plausible carriers for the extended red emission (ERE), a photoluminescent process associated with a wide variety of interstellar environments. Extensive efforts have been devoted over the past two decades to characterize the physical and chemical properties of PAH molecules and ions in space. Absorption spectra of PAH molecules and ions trapped in solid matrices have been compared to the DIBs. Absorption spectra of several cold, isolated gas-phase PAHs have also been measured under experimental conditions that mimic the interstellar conditions. The purpose of this study is to provide a new dimension to the existing spectroscopic database of neutral and single ionized PAHs that is largely based on absorption spectra by adding emission spectroscopy data. The measurements are based on the laser induced fluorescence (LIF) technique and are performed with the Pulsed Discharge Nozzle (PDN) of the COSmIC laboratory facility at NASA Ames laboratory. The PDN generates a plasma in a free supersonic jet expansion to simulate the physical and the chemical conditions in interstellar environments. We focus, here, on the fluorescence spectra of large neutral PAHs and their cations where there is a lack of fluorescence spectroscopy data. The astronomical implications of the data (e.g., ERE) are examined.

  18. Experimental and theoretical comparison of the O K-edge nonresonant inelastic X-ray scattering and X-ray absorption spectra of NaReO4.

    PubMed

    Bradley, Joseph A; Yang, Ping; Batista, Enrique R; Boland, Kevin S; Burns, Carol J; Clark, David L; Conradson, Steven D; Kozimor, Stosh A; Martin, Richard L; Seidler, Gerald T; Scott, Brian L; Shuh, David K; Tyliszczak, Tolek; Wilkerson, Marianne P; Wolfsberg, Laura E

    2010-10-06

    Accurate X-ray absorption spectra (XAS) of first row atoms, e.g., O, are notoriously difficult to obtain due to the extreme sensitivity of the measurement to surface contamination, self-absorption, and saturation affects. Herein, we describe a comprehensive approach for determining reliable O K-edge XAS data for ReO(4)(1-) and provide methodology for obtaining trustworthy and quantitative data on nonconducting molecular systems, even in the presence of surface contamination. This involves comparing spectra measured by nonresonant inelastic X-ray scattering (NRIXS), a bulk-sensitive technique that is not prone to X-ray self-absorption and provides exact peak intensities, with XAS spectra obtained by three different detection modes, namely total electron yield (TEY), fluorescence yield (FY), and scanning transmission X-ray microscopy (STXM). For ReO(4)(1-), TEY measurements were heavily influenced by surface contamination, while the FY and STXM data agree well with the bulk NRIXS analysis. These spectra all showed two intense pre-edge features indicative of the covalent interaction between the Re 5d and O 2p orbitals. Density functional theory calculations were used to assign these two peaks as O 1s excitations to the e and t(2) molecular orbitals that result from Re 5d and O 2p covalent mixing in T(d) symmetry. Electronic structure calculations were used to determine the amount of O 2p character (%) in these molecular orbitals. Time dependent-density functional theory (TD-DFT) was also used to calculate the energies and intensities of the pre-edge transitions. Overall, under these experimental conditions, this analysis suggests that NRIXS, STXM, and FY operate cooperatively, providing a sound basis for validation of bulk-like excitation spectra and, in combination with electronic structure calculations, suggest that NaReO(4) may serve as a well-defined O K-edge energy and intensity standard for future O K-edge XAS studies.

  19. Aprotic solvents effect on the UV-visible absorption spectra of bixin.

    PubMed

    Rahmalia, Winda; Fabre, Jean-François; Usman, Thamrin; Mouloungui, Zéphirin

    2014-10-15

    We describe here the effects of aprotic solvents on the spectroscopic characteristics of bixin. Bixin was dissolved in dimethyl sulfoxide, acetone, dichloromethane, ethyl acetate, chloroform, dimethyl carbonate, cyclohexane and hexane, separately, and its spectra in the resulting solutions were determined by UV-visible spectrophotometry at normal pressure and room temperature. We analyzed the effect of aprotic solvents on λmax according to Onsager cavity model and Hansen theory, and determined the approximate absorption coefficient with the Beer-Lambert law. We found that the UV-visible absorption spectra of bixin were found to be solvent dependent. The S0→S2 transition energy of bixin in solution was dependent principally on the refractive index of the solvents and the bixin-solvent dispersion interaction. There was a small influence of the solvents dielectric constant, permanent dipole interaction and hydrogen bonding occurred between bixin and solvents. The absorbance of bixin in various solvents, with the exception of hexane, increased linearly with concentration. Copyright © 2014 Elsevier B.V. All rights reserved.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Penfold, T. J.; Ecole polytechnique Federale de Lausanne, Laboratoire de chimie et biochimie computationnelles, ISIC, FSB-BCH, CH-1015 Lausanne; SwissFEL, Paul Scherrer Inst, CH-5232 Villigen

    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 rheniummore » 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.« less

  1. First-Principles Predictions of Near-Edge X-ray Absorption Fine Structure Spectra of Semiconducting Polymers

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Su, Gregory M.; Patel, Shrayesh N.; Pemmaraju, C. D.

    The electronic structure and molecular orientation of semiconducting polymers in thin films determine their ability to transport charge. Methods based on near-edge X-ray absorption fine structure (NEXAFS) spectroscopy can be used to probe both the electronic structure and microstructure of semiconducting polymers in both crystalline and amorphous films. However, it can be challenging to interpret NEXAFS spectra on the basis of experimental data alone, and accurate, predictive calculations are needed to complement experiments. Here, we show that first-principles density functional theory (DFT) can be used to model NEXAFS spectra of semiconducting polymers and to identify the nature of transitions inmore » complicated NEXAFS spectra. Core-level X-ray absorption spectra of a set of semiconducting polymers were calculated using the excited electron and core-hole (XCH) approach based on constrained-occupancy DFT. A comparison of calculations on model oligomers and periodic structures with experimental data revealed the requirements for accurate prediction of NEXAFS spectra of both conjugated homopolymers and donor–acceptor polymers. The NEXAFS spectra predicted by the XCH approach were applied to study molecular orientation in donor–acceptor polymers using experimental spectra and revealed the complexity of using carbon edge spectra in systems with large monomeric units. The XCH approach has sufficient accuracy in predicting experimental NEXAFS spectra of polymers that it should be considered for design and analysis of measurements using soft X-ray techniques, such as resonant soft X-ray scattering and scanning transmission X-ray microscopy.« less

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Elliott, Drew; Scime, Earl; Short, Zachary, E-mail: zdshort@mix.wvu.edu

    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 sectionsmore » of xenon and hydrogen is 0.024 ± 0.001.« less

  3. Recording of absorption spectra by a three-beam integral technique with a tunable laser and external cavity

    NASA Astrophysics Data System (ADS)

    Korolenko, P. V.; Nikolaev, I. V.; Ochkin, V. N.; Tskhai, S. N.

    2014-04-01

    An integral method is considered for recording absorption using three laser beams transmitted through and reflected from an external cavity with the absorbing medium (R-ICOS). The method is the elaboration of a known single-beam ICOS method and allows suppression of the influence of radiation phase fluctuations in the resonator on recording weak absorption spectra. First of all, this reduces high-frequency instabilities and gives a possibility to record spectra during short time intervals. In this method, mirrors of the resonator may have moderate reflection coefficients. Capabilities of the method have been demonstrated by the examples of weak absorption spectra of atmospheric methane and natural gas in a spectral range around 1650 nm. With the mirrors having the reflection coefficients of 0.8-0.99, a spectrum can be recorded for 320 μs with the accuracy sufficient for detecting a background concentration of methane in atmosphere. For the acquisition time of 20 s, the absorption coefficients of ~2×10-8 cm-1 can be measured, which corresponds to a 40 times less molecule concentration than the background value.

  4. 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

  5. Laser line illumination scheme allowing the reduction of background signal and the correction of absorption heterogeneities effects for fluorescence reflectance imaging.

    PubMed

    Fantoni, Frédéric; Hervé, Lionel; Poher, Vincent; Gioux, Sylvain; Mars, Jérôme I; Dinten, Jean-Marc

    2015-10-01

    Intraoperative fluorescence imaging in reflectance geometry is an attractive imaging modality as it allows to noninvasively monitor the fluorescence targeted tumors located below the tissue surface. Some drawbacks of this technique are the background fluorescence decreasing the contrast and absorption heterogeneities leading to misinterpretations concerning fluorescence concentrations. We propose a correction technique based on a laser line scanning illumination scheme. We scan the medium with the laser line and acquire, at each position of the line, both fluorescence and excitation images. We then use the finding that there is a relationship between the excitation intensity profile and the background fluorescence one to predict the amount of signal to subtract from the fluorescence images to get a better contrast. As the light absorption information is contained both in fluorescence and excitation images, this method also permits us to correct the effects of absorption heterogeneities. This technique has been validated on simulations and experimentally. Fluorescent inclusions are observed in several configurations at depths ranging from 1 mm to 1 cm. Results obtained with this technique are compared with those obtained with a classical wide-field detection scheme for contrast enhancement and with the fluorescence by an excitation ratio approach for absorption correction.

  6. 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

  7. The inner filter effects and their correction in fluorescence spectra of salt marsh humic matter.

    PubMed

    Mendonça, Ana; Rocha, Ana C; Duarte, Armando C; Santos, Eduarda B H

    2013-07-25

    The inner filter effects in synchronous fluorescence spectra (Δλ=60 nm) of sedimentary humic substances from a salt marsh were studied. Accordingly to their type and the influence of plant colonization, these humic substances have different spectral features and the inner filter effects act in a different manner. The fluorescence spectra of the humic substances from sediments with colonizing plants have a protein like band (λexc=280 nm) which is strongly affected by primary and secondary inner filter effects. These effects were also observed for the bands situated at longer wavelengths, i.e., at λexc=350 nm and λex=454 nm for the fulvic acids (FA) and humic acids (HA), respectively. However, they are more important for the band at 280 nm, causing spectral distortions which can be clearly seen when the spectra of solutions 40 mg L(-1) of different samples (Dissolved Organic Carbon - DOC~20 mg L(-1)) are compared with and without correction of the inner filter effects. The importance of the spectral distortions caused by inner filter effects has been demonstrated in solutions containing a mixture of model compounds which represent the fluorophores detected in the spectra of sedimentary humic samples. The effectiveness of the mathematical correction of the inner filter effects in the spectra of those solutions and of solutions of sedimentary humic substances was studied. It was observed that inner filter effects in the sedimentary humic substances spectra can be mathematically corrected, allowing to obtain a linear relationship between the fluorescence intensity and humic substances concentration and preventing distortions at concentrations as high as 50 mg L(-1) which otherwise would obscure the protein like band. Copyright © 2013 Elsevier B.V. All rights reserved.

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

    NASA Astrophysics Data System (ADS)

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

    2012-03-01

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

  9. Optical Absorption Spectra of Nuclear Filters Modified by Deposition of Silver Nano- and Microparticles

    NASA Astrophysics Data System (ADS)

    Smolyanskii, A. S.; Kozlova, N. V.; Zheltova, A. V.; Aksyutina, A. S.; Shvedov, A. S.; Lakeev, S. G.

    2015-07-01

    Light scattering and interference patterns are studied in the optical absorption spectra of nuclear filters based on polyethylene terephthalate fi lms modifi ed by dry aerosol deposition of silver nano- and microparticles. Surface plasmon polaritons and localized plasmons formed by the passage of light through porous silver films are found to have an effect on the diffraction and interference modes. The thickness of silver nano- and microparticle coatings on the surface of the nuclear fi lters was determined from the shift in the interference patterns in the optical absorption spectra of the modified nuclear filters relative to the original nuclear filters. A correlation was found between the estimated coating thickness and the average surface roughness of the nuclear filters modified by layers of silver nano- and microparticles.

  10. Theoretical Interpretation of the Fluorescence Spectra of Toluene and P- Cresol

    DTIC Science & Technology

    1994-07-01

    NUMBER OF PAGES Toluene Geometrica 25 p-Cresol Fluorescence Is. PRICE CODE Spectra 17. SECURITY CLASSIFICATION 13. SECURITY CLASSIFICATION 19...State Frequencies of Toluene ................ 19 6 Computed and exp" Ground State Frequencies of p-Cresol ............... 20 7 Correction Factors for...Computed Ground State Vibrational Frequencies ....... 21 8 Computed and Corrected Excited State Frequencies of Toluene ............. 22 9 Computed and

  11. Simulations of absorption spectra of conjugated oligomers: role of planar conformation and aggregation in condensed phase

    NASA Astrophysics Data System (ADS)

    Yuan, Xiang-Ai; Wen, Jin; Zheng, Dong; Ma, Jing

    2018-04-01

    This Review highlights the structure/property relationship underlying the morphology modulation through various factors towards the exploration of light-absorbing materials for efficient utilisation of solar power. Theoretical study using a combination of molecular dynamics imulations and the time-dependent density functional theory demonstrated that the planarity plays an important role in tuning spectral properties of oligomer aggregates. The aggregation-induced blue-shift in absorption spectra of oligothiophenes and the red-shift for oligofluorenols were rationalised in a unified way from the reduced (and increased) content of planar conformations in molecular aggregates. The planarity versus non-planarity of oligomers can be modulated by introduction of alkyl side chain or steric bulky substituents. The substitution with various groups in the ortho-position of azobenzene leads to the distorted backbone, breaking symmetry, and hence the red-shift in spectra, expanding the application in biological systems with visible light absorption. The donor-acceptor substituent groups in conjugated oligomers can increase the degree of planarity, electron delocalisation and polarisation, and charge separation, giving rise to the red-shift in spectra and enhancement in polarisability and charge mobility for device applications. The solvent dependent and pH-sensitive properties and intramolecular hydrogen bonds also caused the shift of absorption spectra with the appearance of planar conformers.

  12. Reflectance and fluorescence spectroscopies in photodynamic therapy

    NASA Astrophysics Data System (ADS)

    Finlay, Jarod C.

    In vivo fluorescence spectroscopy during photodynamic therapy (PDT) has the potential to provide information on the distribution and degradation of sensitizers, the formation of fluorescent photoproducts and changes in tissue autofluorescence induced by photodynamic treatment. Reflectance spectroscopy allows quantification of light absorption and scattering in tissue. We present the results of several related studies of fluorescence and reflectance spectroscopy and their applications to photodynamic dosimetry. First, we develop and test an empirical method for the correction of the distortions imposed on fluorescence spectra by absorption and scattering in turbid media. We characterize the irradiance dependence of the in vivo photobleaching of three sensitizers, protoporphyrin IX (PpIX), Photofrin and mTHPC, in a rat skin model. The photobleaching and photoproduct formation of PpIX exhibit irradiance dependence consistent with singlet oxygen (1O2)-mediated bleaching. The bleaching of mTHPC occurs in two phases, only one of which is consistent with a 1O 2-mediated mechanism. Photofrin's bleaching is independent of irradiance, although its photoproduct formation is not. This can be explained by a mixed-mechanism bleaching model. Second, we develop an algorithm for the determination of tissue optical properties using diffuse reflectance spectra measured at a single source-detector separation and demonstrate the recovery of the hemoglobin oxygen dissociation curve from tissue-simulating phantoms containing human erythrocytes. This method is then used to investigate the heterogeneity of oxygenation response in murine tumors induced by carbogen inhalation. We find that while the response varies among animals and within each tumor, the majority of tumors exhibit an increase in blood oxygenation during carbogen breathing. We present a forward-adjoint model of fluorescence propagation that uses the optical property information acquired from reflectance spectroscopy to

  13. Near-edge X-ray absorption spectra for metallic Cu and Mn

    NASA Astrophysics Data System (ADS)

    Greaves, G. N.; Durham, P. J.; Diakun, G.; Quinn, P.

    1981-11-01

    The measurement of X-ray absorption fine structure of metals- both in the extended region (EXAFS) as well as in the near edge region (XANES)-has been widely discussed (see refs 1-6 for Cu and refs 7-9 for Mn). The recent availability of intense X-ray fluxes from storage rings has usually been exploited for EXAFS leaving the XANES often with poorer resolution than earlier work performed on conventional sources (for example, compare the near edge structure for copper in ref. 1 with refs 3 or 6). In addition, whilst the theory and analysis of EXAFS is relatively well-established2,10, a theory for the strong scattering regime near to the absorption edge has only recently been developed11. We report here the first high resolution XANES spectra for Cu and Mn which were performed at the SRS storage ring at Daresbury. Although both metals have close-packed structures consisting of atoms of similar size their local atomic structure is different in detail. Significant differences are found in their respective XANES reflecting the senstivity of this region of the X-ray absorption fine structure to the local atomic structure. Spectra for the two metals have been analysed using the new multiple scattering formalism. This is a real space calculation and unlike a conventional band structure approach it does not require structural periodicity but works from the local arrangement of atoms.

  14. Assessment of the Fluorescence Spectra Characteristics of Dissolved Organic Matter Derived from Organic Waste Composting Based on Projection Pursuit Classification (PPC).

    PubMed

    Wei, Zi-min; Wang, Xing-lei; Pan, Hong-wei; Zhao, Yue; Xie, Xin-yu; Zhao, Yi; Zhang, Lin-xue; Zhao, Tao-zhi

    2015-10-01

    The characteristics of fluorescence spectra of dissolved organic matter (DOM) derived from composting is one of the key ways to assess the compost maturity. However, the existing methods mainly focus on the qualitative description for the humification degree of compost. In this paper, projection pursuit classification (PPC) was conducted to quantitative assess the grades of compost maturity, based on the characteristics of fluorescence spectra of DOM. Eight organic wastes (chicken manure, swine manure, kitchen waste, lawn waste, fruits and vegetables waste, straw, green waste, and municipal solid waste) composting were conducted, the germination percentage (GI) and fluorescence spectra of DOM were measured during composting. Statistic analysis with all fluorescence parameters of DOM indicated that I436/I383 (a ratio between the fluorescence intensities at 436 and 383 nm in excitation spectra), FLR (an area ratio between fulvic-like region from 308 to 363 nm and total region in emission spectra), P(HA/Pro) (a regional integration ratio between humic acid-like region to protein-like region in excitation emission matrix (EEM) spectra), A4/A1 (an area ratio of the last quarter to the first quarter in emission spectra), r(A,C) (a ratio between the fluorescence intensities of peak A and peak C in EEM spectra) were correlated with each other (p < 0.01), suggesting that this fluorescence parameters could be considered as comprehensive evaluation index system of PPC. Subsequently, the four degrades of compost maturity included the best degree of maturity (I, GI > 80%), better degree of compost maturity (II, 60% < GI < 80%), maturity (III, 50% < GI < 60%), and immaturity (IV, GI < 50%) were divided according the GI value during composting. The corresponding fluorescence parameter values were calculated at each degrade of compost maturity. Then the projection values were calculated based on PPC considering the above fluorescence parameter values. The projection value was 2

  15. Synthesis and spectral properties of Methyl-Phenyl pyrazoloquinoxaline fluorescence emitters: Experiment and DFT/TDDFT calculations

    NASA Astrophysics Data System (ADS)

    Gąsiorski, P.; Matusiewicz, M.; Gondek, E.; Uchacz, T.; Wojtasik, K.; Danel, A.; Shchur, Ya.; Kityk, A. V.

    2018-01-01

    Paper reports the synthesis and spectroscopic studies of two novel 1-Methyl-3-phenyl-1H-pyrazolo[3,4-b]quinoxaline (PQX) derivatives with 6-substituted methyl (MeMPPQX) or methoxy (MeOMPPQX) side groups. The optical absorption and fluorescence emission spectra are recorded in solvents of different polarity. Steady state and time-resolved spectroscopy provide photophysical characterization of MeMPPQX and MeOMPPQX dyes as materials for potential luminescence or electroluminescence applications. Measured optical absorption and fluorescence emission spectra are compared with quantum-chemical DFT/TDDFT calculations using long-range corrected xc-functionals, LRC-BLYP and CAM-B3LYP in combination with self-consistent reaction field model based on linear response (LR), state specific (SS) or corrected linear response (CLR) solvations. Performances of relevant theoretical models and approaches are compared. The reparameterized LRC-BLYP functional (ω = 0.231 Bohr-1) in combination with CLR solvation provides most accurate prediction of both excitation and emission energies. The MeMPPQX and MeOMPPQX dyes represent efficient fluorescence emitters in blue-green region of the visible spectra.

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

    NASA Technical Reports Server (NTRS)

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

    1981-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

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

  18. Fluorescence x-ray absorption fine structure studies of Fe-Ni-S and Fe-Ni-Si melts to 1600 K

    NASA Astrophysics Data System (ADS)

    Manghnani, M. H.; Hong, X.; Balogh, J.; Amulele, G.; Sekar, M.; Newville, M.

    2008-04-01

    We report NiK -edge fluorescence x-ray absorption fine structure spectra (XAFS) for Fe0.75Ni0.05S0.20 and Fe0.75Ni0.05Si0.20 ternary alloys from room temperature up to 1600 K. A high-temperature furnace designed for these studies incorporates two x-ray transparent windows and enables both a vertical orientation of the molten sample and a wide opening angle, so that XAFS can be measured in the fluorescence mode with a detector at 90° with respect to the incident x-ray beam. An analysis of the Ni XAFS data for these two alloys indicates different local structural environments for Ni in Fe0.75Ni0.05S0.20 and Fe0.75Ni0.05Si0.20 melts, with more Ni-Si coordination than Ni-S coordination persisting from room temperature through melting. These results suggest that light elements such as S and Si may impact the structural and chemical properties of Fe-Ni alloys with a composition similar to the earth’s core.

  19. Equilibrium Structures and Absorption Spectra for SixOy-nH2O Molecular Clusters using Density Functional Theory

    DTIC Science & Technology

    2017-05-04

    Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/6390--17-9723 Equilibrium Structures and Absorption Spectra for SixOy-nH2O Molecular...Absorption Spectra for SixOy-nH2O Molecular Clusters using Density Functional Theory L. Huang, S.G. Lambrakos, and L. Massa1 Naval Research Laboratory, Code...and time-dependent density functional theory (TD-DFT). The size of the clusters considered is relatively large compared to those considered in

  20. Polarized electronic absorption spectra of Cr2SiO4 single crystals

    NASA Astrophysics Data System (ADS)

    Furche, A.; Langer, K.

    Polarized electronic absorption spectra, E∥a(∥X), E∥b(∥Y) and E∥c(∥Z), in the energy range 3000-5000 cm-1 were obtained for the orthorhombic thenardite-type phase Cr2SiO4, unique in its Cr2+-allocation suggesting some metal-metal bonding in Cr2+Cr2+ pairs with Cr-Cr distance 2.75 Å along [001]. The spectra were scanned at 273 and 120 K on single crystal platelets ∥(100), containing optical Y and Z, and ∥(010), containing optical X and Z, with thicknesses 12.3 and 15.6 μm, respectively. Microscope-spectrometric techniques with a spatial resolution of 20 μm and 1 nm spectral resolution were used. The orientations were obtained by means of X-ray precession photographs. The xenomorphic, strongly pleochroic crystal fragments (X deeply greenish-blue, Y faint blue almost colourless, Z deeply purple almost opaque) were extracted from polycrystalline Cr2SiO4, synthesized at 35 kbar, above 1440 °C from high purity Cr2O3, Cr (10% excess) and SiO2 in chromium capsules. The Cr2SiO4-phase was identified by X-ray diffraction (XRD). Four strongly polarized bands, at about 13500 (I), 15700 (II), 18700 (III) and 19700 (IV) cm-1, in the absorption spectra of Cr2SiO4 single crystals show properties (temperature behaviour of linear and integral absorption coefficients, polarization behaviour, molar absorptivities) which are compatible with an assignment to localized spin-allowed transitions of Cr2+ in a distorted square planar coordination of point symmetry C2. The crystal field parameter of Cr2+ is estimated to be 10 Dq =10700 cm-1. A relatively intense, sharp band at 18400 cm-1 and three other minor features can, from their small half widths, be assigned to spin-forbidden dd-transitions of Cr2+. The intensity of such bands strongly decreases on decreasing temperature. The large half widths, near 5000 cm-1 of band III are indicative of some Cr-Cr interactions, i.e. δ-δ* transitions of Cr24+, whereas the latter alone would be in conflict with the strong

  1. Simultaneous measurement of displacement current and absorption spectra of Langmuir film

    NASA Astrophysics Data System (ADS)

    Xu, Xiaobin; Kubota, Tohru; Iwamoto, Mitsumasa

    1995-07-01

    A Maxwell-displacement-current measuring system coupled with the system used for the measurement of absorption spectra of monolayers on a water surface has been developed. Using this system, the displacement current and the absorbance across monolayers of squarylium dye at the air/water surface were detected. It was found that the change in J aggregate in the monolayers with monolayer compression was detectable using the system.

  2. 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.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Liu, W. L.; Zheng, Z. R.; Liu, Z. G.

    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 becausemore » 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.« less

  4. Fast Decomposition of Three-Component Spectra of Fluorescence Quenching by White and Grey Methods of Data Modeling.

    PubMed

    Kałka, Andrzej J; Turek, Andrzej M

    2018-04-03

    'White' and 'grey' methods of data modeling have been employed to resolve the heterogeneous fluorescence from a fluorophore mixture of 9-cyanoanthracene (CNA), 10-chloro-9-cyanoanthracene (ClCNA) and 9,10-dicyanoanthracene (DCNA) into component individual fluorescence spectra. The three-component spectra of fluorescence quenching in methanol were recorded for increasing amounts of lithium bromide used as a quencher. The associated intensity decay profiles of differentially quenched fluorescence of single components were modeled on the basis of a linear Stern-Volmer plot. These profiles are necessary to initiate the fitting procedure in both 'white' and 'grey' modeling of the original data matrices. 'White' methods of data modeling, called also 'hard' methods, are based on chemical/physical laws expressed in terms of some well-known or generally accepted mathematical equations. The parameters of these models are not known and they are estimated by least squares curve fitting. 'Grey' approaches to data modeling, also known as hard-soft modeling techniques, make use of both hard-model and soft-model parts. In practice, the difference between 'white' and 'grey' methods lies in the way in which the 'crude' fluorescence intensity decays of the mixture components are estimated. In the former case they are given in a functional form while in the latter as digitized curves which, in general, can only be obtained by using dedicated techniques of factor analysis. In the paper, the initial values of the Stern-Volmer constants of pure components were evaluated by both 'point-by-point' and 'matrix' versions of the method making use of the concept of wavelength dependent intensity fractions as well as by the rank annihilation factor analysis applied to the data matrices of the difference fluorescence spectra constructed in two ways: from the spectra recorded for a few excitation lines at the same concentration of a fluorescence quencher or classically from a series of the spectra

  5. Facile synthesis of a two-photon fluorescent probe based on pyrimidine 2-isothiocyanate and its application in bioimaging.

    PubMed

    Yang, Jie; Hu, Wei; Li, Huirong; Hou, Hanna; Tu, Yi; Liu, Bo

    2018-04-18

    Two-photon microscopy imaging has been widely applied in biological imaging, but the development of two-photon absorption probes is obviously lagging behind in the development of imaging technology. In this paper, a two-photon fluorescent probe (1) based on pyrimidine 2-isothiocyanate has been designed and synthesized through a simple method for two-photon biological imaging. Probe 1 was able to couple effectively with the amino groups on biomolecules. To verify the reactivity of the isothiocyanate group on probe 1 and the amine groups on the biomolecules, d-glucosamine was chosen as a model biomolecule to conjugate with probe 1. The result showed that probe 1 could effectively conjugate with d-glucosamine to synthesize probe 2, and the yield of probe 2 was 83%. After conjugating with d-glucosamine, linear absorption spectra, single-photon fluorescence spectra, and two-photon fluorescence spectra of probes 1 and 2 did not present significant changes. Probes 1 and 2 exhibited high fluorescence quantum yields (0.71-0.79) in toluene and chloroform. They also exhibited different photo-physical properties in solvents with different polarities. The two-photon absorption cross-section of probe 1 was 953 GM in toluene. In addition, probe 1 could be effectively conjugated with transferrin, and the conjugated probe (Tf-1) could be transported into Hep G2 cells through a receptor-mediated process for biological imaging. These results demonstrate that such probes are expected to have great potential applications in two-photon fluorescence bioimaging.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Gustavsson, Thomas; Coto, Pedro B.; Serrano-Andres, Luis

    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.

  7. Action Spectra for Nitrate and Nitrite Assimilation in Blue-Green Algae 1

    PubMed Central

    Serrano, Aurelio; Losada, Manuel

    1988-01-01

    Action spectra for the assimilation of nitrate and nitrite have been obtained for several blue-green algae (cyanobacteria) with different accessory pigment composition. The action spectra for both nitrate and nitrite utilization by nitrate-grown Anacystis nidulans L-1402-1 cells exhibited a clear peak at about 620 nanometers, corresponding to photosystem II (PSII) C-phycocyanin absorption, the contribution of chlorophyll a (Chl a) being barely detectable. The action spectrum for nitrate reduction by a nitrite reductase mutant of A. nidulans R2 was very similar. All these action spectra resemble the fluorescence excitation spectrum of cell suspensions of the microalgae monitored at 685 nanometers—the fluorescence band of Chl a in PSII. In contrast, the action spectrum for nitrite utilization by nitrogen-starved A. nidulans cells, which are depleted of C-phycocyanin, showed a maximum near 680 nanometers, attributable to Chl a absorption. The action spectrum for nitrite utilization by Calothrix sp. PCC 7601 cells, which contain both C-phycoerythrin and C-phycocyanin as PSII accessory pigments, presented a plateau in the region from 550 to 630 nanometers. In this case, there was also a clear parallelism between the action spectrum and the fluorescence excitation spectrum, which showed two overlapped peaks with maxima at 562 and 633 nanometers. The correlation observed between the action spectra for both nitrate and nitrite assimilation and the light-harvesting pigment content of the blue-green algae studied strongly suggests that phycobiliproteins perform a direct and active role in these photosynthetic processes. PMID:16666041

  8. Optical and structural properties of plasma-treated Cordyceps bassiana spores as studied by circular dichroism, absorption, and fluorescence spectroscopy

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lee, Geon Joon, E-mail: gjlee@kw.ac.kr; Sim, Geon Bo; Choi, Eun Ha

    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 watermore » (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.« less

  9. 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.

  10. 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.

  11. 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...

  12. Detection of absorption lines in the spectra of X-ray bursts from X1608-52

    NASA Astrophysics Data System (ADS)

    Nakamura, Norio; Inoue, Hajime; Tanaka, Yasuo

    X-ray bursts from X 1608-52 were observed with the gas scintillation proportional counters on the Tenma satellite. Absorption features were detected in the spectra of three bursts among 17 bursts observed. These absorption features are consistent with a common absorption line at 4.1 keV. The energy and the properties of the absorption lines of the X 1608-52 bursts are very similar to those observed from the X 1636-53 bursts by Waki et al. (1984). Near equality of the absorption-line energies for X 1636-53 and X 1608-52 would imply that mass and radius of the neutron stars in these two systems are very similar to each other.

  13. Potential benefits of triethylamine as n-electron donor in the estimation of forskolin by electronic absorption and emission spectroscopy

    NASA Astrophysics Data System (ADS)

    Raju, Gajula; Ram Reddy, A.

    2016-02-01

    Diterpenoid forskolin was isolated from Coleus forskolii. The electronic absorption and emission studies of forskolin were investigated in various solvents with an aim to improve its detection limits. The two chromophores present in the diterpenoid are not conjugated leading to the poor absorption and emission of UV light. The absorption and fluorescence spectra were solvent specific. In the presence of a monodentate ligand, triethylamine the detection of forskolin is improved by 3.63 times in ethanol with the fluorescence method and 3.36 times in DMSO by the absorption spectral method. The longer wavelength absorption maximum is blue shifted while the lower energy fluorescence maximum is red shifted in the presence of triethylamine. From the wavelength of fluorescence maxima of the exciplex formed between excited forskolin and triethylamine it is concluded that the order of reactivity of hydroxyl groups in the excited state forskolin is in the reverse order to that of the order of the reactivity of hydroxyl groups in its ground state.

  14. [Study on the deteriorating course of fresh milk by laser-induced fluorescence spectra].

    PubMed

    Liu, J; Yu, C Q; Li, J Z; Yan, J X

    2001-12-01

    Along with the development of living standard, people's demand for food quality and food hygiene also rises. People demand food not only with rich nutrition, inexpensive price, but also with safety. So food hygiene test is paid common attention of society. Milk is a nourishing food and is loved by people. Sour milk goods from milk is also in great demand. But nourishing foods are good for growing many microbes. Fresh milk and sour milk are easy contaminated by microbes and go bad. Laser-induced fluorescence (LIF) technology is an important part of modern optics. It is broadly applied in biomedicine, diagnostics, test of food hygiene, environment protecting, owing to its high sensitivity, high speed, automation, untouched testing. In this paper, we attempted to LIF technology to test milk food quality. We used the third harmonics pulsed Nd:YAG laser (355 nm) as the exciting source, and a multi-track spectrometer as the detector and measured the intensities of apply LIF of fresh milk and sour milk during their deteriorating course. Test system and test method are introduced, fluorescence spectra of deteriorating course are also attached. The test result makes clear that there are close connection between deteriorating course and fluorescence spectra.

  15. Determination of total x-ray absorption coefficient using non-resonant x-ray emission

    PubMed Central

    Achkar, A. J.; Regier, T. Z.; Monkman, E. J.; Shen, K. M.; Hawthorn, D. G.

    2011-01-01

    An alternative measure of x-ray absorption spectroscopy (XAS) called inverse partial fluorescence yield (IPFY) has recently been developed that is both bulk sensitive and free of saturation effects. Here we show that the angle dependence of IPFY can provide a measure directly proportional to the total x-ray absorption coefficient, µ(E). In contrast, fluorescence yield (FY) and electron yield (EY) spectra are offset and/or distorted from µ(E) by an unknown and difficult to measure amount. Moreover, our measurement can determine µ(E) in absolute units with no free parameters by scaling to µ(E) at the non-resonant emission energy. We demonstrate this technique with measurements on NiO and NdGaO3. Determining µ(E) across edge-steps enables the use of XAS as a non-destructive measure of material composition. In NdGaO3, we also demonstrate the utility of IPFY for insulating samples, where neither EY or FY provide reliable spectra due to sample charging and self-absorption effects, respectively. PMID:22355697

  16. Thioflavin T as an efficient fluorescence sensor for selective recognition of RNA G-quadruplexes

    NASA Astrophysics Data System (ADS)

    Xu, Shujuan; Li, Qian; Xiang, Junfeng; Yang, Qianfan; Sun, Hongxia; Guan, Aijiao; Wang, Lixia; Liu, Yan; Yu, Lijia; Shi, Yunhua; Chen, Hongbo; Tang, Yalin

    2016-04-01

    RNA G-quadruplexes (G4s) play important roles in translational regulation, mRNA processing events and gene expression. Therefore, a fluorescent probe that is capable of efficiently recognizing RNA G-quadruplex structures among other RNA forms is highly desirable. In this study, a water-soluble fluorogenic dye (i.e., Thioflavin T (ThT)) was employed to recognize RNA G-quadruplex structures using UV-Vis absorption spectra, fluorescence spectra and emission lifetime experiments. By stacking on the G-tetrad, the ThT probe exhibited highly specific recognition of RNA G-quadruplex structures with striking fluorescence enhancement compared with other RNA forms. The specific binding demonstrates that ThT is an efficient fluorescence sensor that can distinguish G4 and non-G4 RNA structures.

  17. Numerical indicators of absorption spectra of green leaf extract obtained from plants of different life forms.

    PubMed

    Koldaev, Vladimir M; Manyakhin, Artem Yu

    2018-06-05

    The study was carried out using 58 species of terrestrial plants of different life forms at the start of their fruiting stage. Photoreceptive systems of the leaves were assessed by means of unconventional numerical indicators of absorption spectra, relative photoabsorption coefficient, photosynthetic pigments' integral absorption intensity and relative absorption intensity coefficient. As the study showed, the leaves of all trees and light-demanding grasses favoring open spaces, which were subjected to the study were featured by the lowest values of numerical indicators of absorption spectra (NIAS). Shade-demanding grasses, which grow beneath the canopy, by contrast, were featured by the highest NIAS values. These values of the shrub leaves were in between those of light-demanding plants and shade-demanding ones. The results obtained are consistent with modern visions concerning the biochemistry and the physiology of plants' photoreceptive system. It is appropriate to apply the NIAS, which were used in this study and reflect a leaf's photoreceptive properties, as spectrophotometric criteria for monitoring and environmental management of natural plant resources and agricultural plants. Copyright © 2018 Elsevier B.V. All rights reserved.

  18. Absorption and fluorescence properties of colored dissolved organic matter in the Ross Sea during austral summer

    NASA Astrophysics Data System (ADS)

    D'Sa, E. J.; Kim, H. C.; Ha, S. Y.

    2016-12-01

    Colored dissolved organic matter (CDOM) spectral absorption and excitation-emission matrix (EEMs) fluorescence with parallel factor analysis (PARAFAC) were examined in the Ross Sea during a survey conducted on board the R/V Araon in the austral summer of 14/15. CDOM absorption at 355 nm ranged from 0.06 to 1.14 m-1 while spectral slope S calculated between 275-295 nm wavelength ranged from 18.83 to 33.32 µm-1 with water masses playing an important role in its variability. Spectral slope S decreased with increasing CDOM absorption indicating the strong role of photo-oxidation on CDOM abundance during the summer. PARAFAC analysis of EEM data identified two humic-like (terrestrial and marine-like) and a protein-like (tryptophan-like) component. The two humic-like components were well correlated with little variability spatially and across the water column ( 0-100 m) likely indicating more refractory material. The protein-like fluorescent component was relatively quite variable supporting the autochthonous production of this fluorescent component in the highly productive Ross Sea waters.

  19. Transient Fluorescence Spectroscopy and laser induced fluorescence lifetimes of terbium doped dipicolinic acid

    NASA Astrophysics Data System (ADS)

    Makoui, Anali

    We have investigated the use of deep UV laser induced fluorescence for the sensitive detection and spectroscopic lifetime studies of terbium doped dipicolinic acid (DPA-Tb) and used this to study the optical characteristics of DPA which is a chemical surrounding most bacterial spores. Background absorption spectra, fluorescence spectra, and Excitation Emission Matrix (EEM) spectra were made of the DPA-Tb complex, using both fixed 266 nm wavelength and tunable (220 nm--280 nm) UV laser excitations. Of importance, the fluorescence lifetimes of the four main fluorescence peaks (488 nm, 543 nm, 581 nm, and 618 nm) of the DPA-Tb complex have been measured for the first time to our knowledge. The lifetimes of all the fluorescing lines have been measured as a function of DPA-Tb concentration, solvent pH, and solvent composition, including that for the weakest fluorescing line of DPA-Tb at 618 nm. In addition, a new spectroscopic lifetime measurement technique, which we call "Transient Fluorescence Spectroscopy", was developed. In this technique, a weak, quasi-CW, amplitude modulated UV laser (8.5 kHz) was used to measure the lifetimes of the fluorescence lines, and yields insight into energy transfer and excitation lifetimes within the system. This technique is especially useful when a high power laser is not either available or not suitable. In the latter case, this would be when a high power pulsed deep-UV laser could produce bleaching or destruction of the biological specimen. In addition, this technique simulated the excitation and fluorescence emission of the DPA-Tb using a 4-level energy model, and solved the dynamic transient rate equations to predict the temporal behavior of the DPA-Tb emitted fluorescence. Excellent agreement between the experiments and the simulation were found. This technique has the potential to provide a more accurate value for the fluorescence lifetime values. In addition, with the use of asymmetric excitation waveforms, the dynamic

  20. Absorption spectra analysis of hydrated uranium(III) complex chlorides

    NASA Astrophysics Data System (ADS)

    Karbowiak, M.; Gajek, Z.; Drożdżyński, J.

    2000-11-01

    Absorption spectra of powdered samples of hydrated uranium(III) complex chlorides of the formulas NH 4UCl 4 · 4H 2O and CsUCl 4 · 3H 2O have been recorded at 4.2 K in the 4000-26 000 cm -1 range. The analysis of the spectra enabled the determination of crystal-field parameters and assignment of 83 and 77 crystal-field levels for the tetrahydrate and trihydrate, respectively. The energies of the levels were computed by applying a simplified angular overlap model as well as a semiempirical Hamiltonian representing the combined atomic and crystal-field interactions. Ab initio calculations have enabled the application of a simplified parameterization and the determination of the starting values of the AOM parameters. The received results have proved that the AOM approach can quite well predict both the structure of the ground multiplet and the positions of the crystal-field levels in the 17 000-25 000 cm -1 range, usually obscured by strong f-d bands.

  1. Absorption and emission spectroscopic characteristics of dipterex and its molecularly imprinted recognition: A TD-DFT investigation

    NASA Astrophysics Data System (ADS)

    Cheng, Xueli; Li, Liqing; Zhao, Yanyun; Wang, Chang'an

    2016-05-01

    By using G09 program package, the absorption and fluorescence/phosphorescence spectra of dipterex were explored, and its spectroscopic characters were altered by methacrylic acid (MAA) as the imprinted molecule. The TD-DFT results revealed that: (1) All absorption and emission excitations of dipterex are assigned to the nσ∗ transition; (2) without MAA as imprinted molecule, one of the dipterex Csbnd Cl bonds is extended significantly and dipterex is almost destroyed in transition states; (3) dipterex is connected to methacrylic acid via two hydrogen bonds; (4) for the dipterex-MAA complex, the electronic excitation (ππ∗ excitation) in absorption spectra is dominated by the configuration HOMO → LUMO.

  2. Influence of temperature on water and aqueous glucose absorption spectra in the near- and mid-infrared regions at physiologically relevant temperatures.

    PubMed

    Jensen, Peter Snoer; Bak, Jimmy; Andersson-Engels, Stefan

    2003-01-01

    Near- and mid-infrared absorption spectra of pure water and aqueous 1.0 g/dL glucose solutions in the wavenumber range 8000-950 cm-1 were measured in the temperature range 30-42 degrees C in steps of 2 degrees C. Measurements were carried out with an FT-IR spectrometer and a variable pathlength transmission cell controlled within 0.02 degree C. Pathlengths of 50 microns and 0.4 mm were used in the mid- and near-infrared spectral region, respectively. Difference spectra were used to determine the effect of temperature on the water spectra quantitatively. These spectra were obtained by subtracting the 37 degrees C water spectrum from the spectra measured at other temperatures. The difference spectra reveal that the effect of temperature is highest in the vicinity of the strong absorption bands, with a number of isosbestic points with no temperature dependence and relatively flat plateaus in between. On the basis of these spectra, prospects for and limitations on data analysis for infrared diagnostic methods are discussed. As an example, the absorptive properties of glucose were studied in the same temperature range in order to determine the effect of temperature on the spectral shape of glucose. The change in water absorption associated with the addition of glucose has also been studied. An estimate of these effects is given and is related to the expected level of infrared signals from glucose in humans.

  3. Synchronous fluorescence spectroscopic study of solvatochromic curcumin dye

    NASA Astrophysics Data System (ADS)

    Patra, Digambara; Barakat, Christelle

    2011-09-01

    Curcumin, the main yellow bioactive component of turmeric, has recently acquired attention by chemists due its wide range of potential biological applications as an antioxidant, an anti-inflammatory, and an anti-carcinogenic agent. This molecule fluoresces weakly and poorly soluble in water. In this detailed study of curcumin in thirteen different solvents, both the absorption and fluorescence spectra of curcumin was found to be broad, however, a narrower and simple synchronous fluorescence spectrum of curcumin was obtained at Δ λ = 10-20 nm. Lippert-Mataga plot of curcumin in different solvents illustrated two sets of linearity which is consistent with the plot of Stokes' shift vs. the ET30. When Stokes's shift in wavenumber scale was replaced by synchronous fluorescence maximum in nanometer scale, the solvent polarity dependency measured by λSFSmax vs. Lippert-Mataga plot or ET30 values offered similar trends as measured via Stokes' shift for protic and aprotic solvents for curcumin. Better linear correlation of λSFSmax vs. π* scale of solvent polarity was found compared to λabsmax or λemmax or Stokes' shift measurements. In Stokes' shift measurement both absorption/excitation as well as emission (fluorescence) spectra are required to compute the Stokes' shift in wavenumber scale, but measurement could be done in a very fast and simple way by taking a single scan of SFS avoiding calculation and obtain information about polarity of the solvent. Curcumin decay properties in all the solvents could be fitted well to a double-exponential decay function.

  4. Synchronous fluorescence spectroscopic study of solvatochromic curcumin dye.

    PubMed

    Patra, Digambara; Barakat, Christelle

    2011-09-01

    Curcumin, the main yellow bioactive component of turmeric, has recently acquired attention by chemists due its wide range of potential biological applications as an antioxidant, an anti-inflammatory, and an anti-carcinogenic agent. This molecule fluoresces weakly and poorly soluble in water. In this detailed study of curcumin in thirteen different solvents, both the absorption and fluorescence spectra of curcumin was found to be broad, however, a narrower and simple synchronous fluorescence spectrum of curcumin was obtained at Δλ=10-20 nm. Lippert-Mataga plot of curcumin in different solvents illustrated two sets of linearity which is consistent with the plot of Stokes' shift vs. the ET30. When Stokes's shift in wavenumber scale was replaced by synchronous fluorescence maximum in nanometer scale, the solvent polarity dependency measured by λSFSmax vs. Lippert-Mataga plot or ET30 values offered similar trends as measured via Stokes' shift for protic and aprotic solvents for curcumin. Better linear correlation of λSFSmax vs. π* scale of solvent polarity was found compared to λabsmax or λemmax or Stokes' shift measurements. In Stokes' shift measurement both absorption/excitation as well as emission (fluorescence) spectra are required to compute the Stokes' shift in wavenumber scale, but measurement could be done in a very fast and simple way by taking a single scan of SFS avoiding calculation and obtain information about polarity of the solvent. Curcumin decay properties in all the solvents could be fitted well to a double-exponential decay function. Copyright © 2011 Elsevier B.V. All rights reserved.

  5. Quantitative comparison of the absorption spectra of the gas mixtures in analogy to the criterion of Pearson

    NASA Astrophysics Data System (ADS)

    Kistenev, Yu. V.; Kuzmin, D. A.; Sandykova, E. A.; Shapovalov, A. V.

    2015-11-01

    An approach to the reduction of the space of the absorption spectra, based on the original criterion for profile analysis of the spectra, was proposed. This criterion dates back to the known statistics chi-square test of Pearson. Introduced criterion allows to quantify the differences of spectral curves.

  6. Variation in Ambient and 77K Leaf-Level Chlorophyll Fluorescence Spectra of Boreal Species During Spring Recovery of Photosynthesis. Comparison of Methods.

    NASA Astrophysics Data System (ADS)

    Rajewicz, P. A.; Atherton, J.; Porcar-Castell, A.

    2017-12-01

    Chlorophyll fluorescence (ChF) is widely used as a tool for tracking changes in photosynthetic activity. In contrast to traditional active methods, which can be applied to leaf-level studies, new passive fluorescence methods are applied to study the photosynthetic dynamics of whole plants, canopies and ecosystems. A number of open questions still remain as to how the shape and intensity of the fluorescence spectra is connected to the mechanistic acclimation of photosynthesis. This is particularly critical at the leaf-level, which is the smallest scale at which spectral fluorescence can be measured in vivo, and especially for conifer needles which are difficult to measure due to their complex geometry.The goal of our research was to develop a protocol for measuring ambient and 77K spectral fluorescence in intact leaves and to use it for tracking the seasonal dynamics in leaf fluorescence properties across boreal species and different canopy heights, including: two conifers, Pinus silvestris and Picea abies; one broadleaf tree, Betula Pendula; and two ground species: Vaccinium vitis-idaea and Vaccinium myrtillus. This activity was organized as part of the multiscale FAST campaign "Fluorescence Across Space and Time" (February 9th - July 11th 2017, Hyytiälä Forest Station, SMEAR II, Finland).We assessed the impact of using "needle-mats" as a reliable method to track seasonal changes in spectral fluorescence properties of needles. In addition, we developed a spectral box to facilitate the measurement of ambient and 77K temperature fluorescence spectra from exactly the same leaf sample footprint. The resulting data can be used to study the impact of photosystem reorganization on the in vivo spectra. Here we present our findings in regard to the comparison of ambient and 77K fluorescence spectra, which can improve the current understanding of structural photosystems' changes detectable through fluorescence signal.

  7. Molecular hydrogen fluorescence and accretion in far-ultraviolet spectra of classical T Tauri stars

    NASA Astrophysics Data System (ADS)

    Herczeg, Gregory J.

    2005-11-01

    Far-ultraviolet spectra of classical T Tauri stars reveal accretion, outflows, and H 2 fluorescence. The E140M echelle spectrograph on HST /STIS and the FUSE satellite offer high spectral resolution and broad wavelength coverage, and enables our unique and detailed analysis of the H 2 lines. A strong and broad Lya emission line excites warm H 2 into many levels of the B and C electronic states, from which we can detect as many as 200 H 2 emission lines. These H2 lines are narrow and often asymmetric, with excess blueshifted emission that can extend to 100 km s -1 from some sources. The fluorescent H 2 emission probes diverse environments around CTTSs. High spectral and spatial resolution are essential for identifying the location and studying the kinematics of the gas, which constrain the origin of the H 2 emission. Several other spectral characteristics, including absorption of H2 emission by the wind and H 2 absorption lines, also provide valuable diagnostics of the origin of this emission. The H 2 emission is most likely produced at the surface of a circumstellar disk in some sources, but is produced by outflows from other sources. DF Tau appears to show H 2 emission from both a disk and an outflow. The excitation of H 2 can be determined from relative line strengths by measuring self-absorption in lines with low-energy lower levels, or by reconstructing the Lya profile incident upon the warm H 2 using the total flux from a single upper level and the opacity in the pumping transition. Based on those diagnostics and the rich H 2 spectrum of TW Hya, the H 2 at the warm disk surface has a column density of log N (H 2 ) = [Special characters omitted.] , a temperature T = [Special characters omitted.] K, and a filling factor of H 2 , as seen by the source of Lya emission, of 0.25 +/- 0.08 (all 2s error bars). The total FUV luminosity from CTTSs ranges from 2 x 10 -3 to 3 x 10 -2 [Special characters omitted.] , much of which is in the Lya line. With the exception of

  8. 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.

  9. Emission from water vapor and absorption from other gases at 5-7.5 μm in Spitzer-IRS Spectra Of Protoplanetary Disks

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Sargent, B. A.; Forrest, W.; Watson, Dan M.

    We present spectra of 13 T Tauri stars in the Taurus-Auriga star-forming region showing emission in Spitzer Space Telescope Infrared Spectrograph 5-7.5 μm spectra from water vapor and absorption from other gases in these stars' protoplanetary disks. Seven stars' spectra show an emission feature at 6.6 μm due to the ν{sub 2} = 1-0 bending mode of water vapor, with the shape of the spectrum suggesting water vapor temperatures >500 K, though some of these spectra also show indications of an absorption band, likely from another molecule. This water vapor emission contrasts with the absorption from warm water vapor seenmore » in the spectrum of the FU Orionis star V1057 Cyg. The other 6 of the 13 stars have spectra showing a strong absorption band, peaking in strength at 5.6-5.7 μm, which for some is consistent with gaseous formaldehyde (H{sub 2}CO) and for others is consistent with gaseous formic acid (HCOOH). There are indications that some of these six stars may also have weak water vapor emission. Modeling of these stars' spectra suggests these gases are present in the inner few AU of their host disks, consistent with recent studies of infrared spectra showing gas in protoplanetary disks.« less

  10. 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.

  11. Ultraviolet absorption spectra of shock-heated carbon dioxide and water between 900 and 3050 K

    NASA Astrophysics Data System (ADS)

    Schulz, C.; Koch, J. D.; Davidson, D. F.; Jeffries, J. B.; Hanson, R. K.

    2002-03-01

    Spectrally resolved UV absorption cross-sections between 190 and 320 nm were measured in shock-heated CO 2 between 880 and 3050 K and H 2O between 1230 and 2860 K. Absorption spectra were acquired with 10 μs time resolution using a unique kinetic spectrograph, thereby enabling comparisons with time-dependent chemical kinetic modeling of post-shock thermal decomposition and chemical reactions. Although room temperature CO 2 is transparent (σ<10 -22 cm2) at wavelengths longer than 200 nm, hot CO 2 has significant absorption (σ>10 -20 cm2) extending to wavelengths longer than 300 nm. The temperature dependence of CO 2 absorption strongly suggests sharply increased transition probabilities from excited vibrational levels.

  12. Improved Charge-Transfer Fluorescent Dyes

    NASA Technical Reports Server (NTRS)

    Meador, Michael

    2005-01-01

    Improved charge-transfer fluorescent dyes have been developed for use as molecular probes. These dyes are based on benzofuran nuclei with attached phenyl groups substituted with, variously, electron donors, electron acceptors, or combinations of donors and acceptors. Optionally, these dyes could be incorporated as parts of polymer backbones or as pendant groups or attached to certain surfaces via self-assembly-based methods. These dyes exhibit high fluorescence quantum yields -- ranging from 0.2 to 0.98, depending upon solvents and chemical structures. The wavelengths, quantum yields, intensities, and lifetimes of the fluorescence emitted by these dyes vary with (and, hence, can be used as indicators of) the polarities of solvents in which they are dissolved: In solvents of increasing polarity, fluorescence spectra shift to longer wavelengths, fluorescence quantum yields decrease, and fluorescence lifetimes increase. The wavelengths, quantum yields, intensities, and lifetimes are also expected to be sensitive to viscosities and/or glass-transition temperatures. Some chemical species -- especially amines, amino acids, and metal ions -- quench the fluorescence of these dyes, with consequent reductions in intensities, quantum yields, and lifetimes. As a result, the dyes can be used to detect these species. Another useful characteristic of these dyes is a capability for both two-photon and one-photon absorption. Typically, these dyes absorb single photons in the ultraviolet region of the spectrum (wavelengths < 400 nm) and emit photons in the long-wavelength ultraviolet, visible, and, when dissolved in some solvents, near-infrared regions. In addition, these dyes can be excited by two-photon absorption at near-infrared wavelengths (600 to 800 nm) to produce fluorescence spectra identical to those obtained in response to excitation by single photons at half the corresponding wavelengths (300 to 400 nm). While many prior fluorescent dyes exhibit high quantum yields

  13. 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.

  14. [Effect of quantum dots CdSe/ZnS's concentration on its fluorescence].

    PubMed

    Jin, Min; Huang, Yu-hua; Luo, Ji-xiang

    2015-02-01

    The authors measured the absorption and the fluorescence spectra of the quantum dots CdSe/ZnS with 4 nm in size at different concentration with the use of the UV-Vis absorption spectroscopy and fluorescence spectrometer. The effect of quantum dots CdSe/ZnS's concentration on its fluorescence was especially studied and its physical mechanism was analyzed. It was observed that the optimal concentration of the quantum dots CdSe/ZnS for fluorescence is 2 micromole x L(-1). When the quantum dot's concentration is over 2 micromol x L(-1), the fluorescence is decreased with the increase in the concentration. While the quantum dot's concentration is less than 2 micromol x L(-1), the fluorescence is decreased with the decrease in the concentration. There are two main reasons: (1) fluorescence quenching and 2) the competition between absorption and fluorescence. When the quantum dot's concentration is over 2 micromol x L(-1), the distance between quantum dots is so close that the fluorescence quenching is induced. The closer the distance between quantum dots is, the more serious the fluorescence quenching is induced. Also, in this case, the absorption is so large that some of the quantum dots can not be excited because the incident light can not pass through the whole sample. As a result, the fluorescence is decreased with the increase in the quantum dot's concentration. As the quantum dot's concentration is below 2 micromol x L(-1), the distance between quantum dots is far enough that no more fluorescence quenching is induced. In this case, the fluorescence is determined by the particle number per unit volume. More particle number per unit volume produces more fluorescence. Therefore, the fluorescence is decreased with the decrease in the quantum dot's concentration.

  15. Structure of fluorescent metal clusters on a DNA template.

    NASA Astrophysics Data System (ADS)

    Vdovichev, A. A.; Sych, T. S.; Reveguk, Z. V.; Smirnova, A. A.; Maksimov, D. A.; Ramazanov, R. R.; Kononov, A. I.

    2016-08-01

    Luminescent metal clusters are a subject of growing interest in recent years due to their bright emission from visible to near infrared range. Detailed structure of the fluorescent complexes of Ag and other metal clusters with ligands still remains a challenging task. In this joint experimental and theoretical study we synthesized Ag-DNA complexes on a DNA oligonucleotide emitting in violet- green spectral range. The structure of DNA template was determined by means of various spectral measurements (CD, MS, XPS). Comparison of the experimental fluorescent excitation spectra and calculated absorption spectra for different QM/MM optimized structures allowed us to determine the detailed structure of the green cluster containing three silver atoms in the stem of the DNA hairpin structure stabilized by cytosine-Ag+-cytosine bonds.

  16. Iodine absorption cells quality evaluation methods

    NASA Astrophysics Data System (ADS)

    Hrabina, Jan; Zucco, Massimo; Holá, Miroslava; Šarbort, Martin; Acef, Ouali; Du-Burck, Frédéric; Lazar, Josef; Číp, Ondřej

    2016-12-01

    The absorption cells represent an unique tool for the laser frequency stabilization. They serve as irreplaceable optical frequency references in realization of high-stable laser standards and laser sources for different brands of optical measurements, including the most precise frequency and dimensional measurement systems. One of the most often used absorption media covering visible and near IR spectral range is molecular iodine. It offers rich atlas of very strong and narrow spectral transitions which allow realization of laser systems with ultimate frequency stabilities in or below 10-14 order level. One of the most often disccussed disadvantage of the iodine cells is iodine's corrosivity and sensitivity to presence of foreign substances. The impurities react with absorption media and cause spectral shifts of absorption spectra, spectral broadening of the transitions and decrease achievable signal-to-noise ratio of the detected spectra. All of these unwanted effects directly influence frequency stability of the realized laser standard and due to this fact, the quality of iodine cells must be precisely controlled. We present a comparison of traditionally used method of laser induced fluorescence (LIF) with novel technique based on hyperfine transitions linewidths measurement. The results summarize advantages and drawbacks of these techniques and give a recommendation for their practical usage.

  17. TD-M06-2X insights into the absorption and emission spectra of dichlorvos and its molecularly imprinted recognition by methacrylic acid.

    PubMed

    Cheng, Xueli

    2016-11-01

    The absorption and emission spectra of dichlorvos and the dichlorvos-MAA complex in methanol, water, and chloroform in the molecularly imprinted recognition were investigated systematically. The M06-2X results revealed that: 1) the hydroxyl groups in polar solvents such as methanol and water may markedly influence the weak interactions, and then alter the adsorption and emission spectra; 2) the electronic excitation in absorption spectra of dichlorvos is dominated by the configuration HOMO → LUMO, but in the most stable dichlorvos-MAA it becomes the ππ* excitation of HOMO → LUMO + 1; 3) Mulliken charges reveal that dichlorvos almost dissociates to Cl - and a cation in its S 1 excitation state; 4) the phosphorescence spectra of dichlorvos-MAA are relatively weak. Graphical Abstract The absorption and emission spectra of dichlorvos and the dichlorvos-MAA complex in the molecularly imprinted recognition of dichlorvos were investigated systematically in methanol, water, and chloroform as solvents.

  18. Controlling photophysics of styrylnaphthalimides through TICT, fluorescence and E,Z-photoisomerization interplay.

    PubMed

    Panchenko, Pavel A; Arkhipova, Antonina N; Fedorova, Olga A; Fedorov, Yuri V; Zakharko, Marina A; Arkhipov, Dmitry E; Jonusauskas, Gediminas

    2017-01-04

    The photophysical properties of naphthalimide dyes NI1-3 with electron releasing 4-methoxy- (NI1), 3,4-dimethoxystyryl- (NI2) and dimethylaminostyryl (NI3) groups are examined in a variety of protic and aprotic solvents. All compounds demonstrate positive solvatochromism in the steady-state absorption and fluorescence spectra. The analysis of the dependence of the Stokes shift on the polarity of the solvent using the Lippert-Mataga equation allowed us to determine the change in the dipole moment upon excitation. The obtained data correspond to the formation of highly polar charge transfer states. Based on the transient absorption spectra and time-resolved fluorescence measurements, the presence of two different emissive states was definitely proved. The primarily formed planar Local Excited (LE) state dominates in non-polar solvents like cyclohexane and toluene where it relaxes mostly through fluorescence and E,Z-isomerisation pathways. In polar solvents, an alternative relaxation channel emerges that consists of twisting around single bond between styryl and naphthalimide fragments, which leads to the formation of a Twisted Intramolecular Charge Transfer (TICT) state. The factors affecting the fluorescence of TICT states are discussed. The observed spectral effects are rationalized using quantum-chemical calculations, X-ray data and NMR spectroscopy.

  19. Synthesis, spectral behaviour and photophysics of donor-acceptor kind of chalcones: Excited state intramolecular charge transfer and fluorescence quenching studies

    NASA Astrophysics Data System (ADS)

    Pannipara, Mehboobali; Asiri, Abdullah M.; Alamry, Khalid A.; Arshad, Muhammad N.; El-Daly, Samy A.

    2015-02-01

    The spectral and photophysical properties of two chalcones containing electron donating and accepting groups with intramolecular charge transfer characteristics were synthesized and characterized by 1H NMR, 13C NMR and X-ray crystallography. Both compounds show very strong solvent polarity dependent changes in their photophysical characteristics, namely, remarkable red shift in the emission spectra with increasing solvent polarity, large change in Stokes shift, significant reduction in the fluorescence quantum yield; indicating that the fluorescence states of these compounds are of intramolecular charge transfer (ICT) character. The solvent effect on the photophysical parameters such as singlet absorption, molar absorptivity, oscillator strength, dipole moment, fluorescence spectra, and fluorescence quantum yield of both compounds have been investigated comprehensively. For both dyes, Lippert-Mataga and Reichardt's correlations were used to estimate the difference between the excited and ground state dipole moments (Δμ). The interactions of dyes with colloidal silver nanoparticles (Ag NPs) were also studied in ethanol using steady state fluorescence quenching measurements. The fluorescence quenching data reveal that dynamic quenching and energy transfer play a major role in the fluorescence quenching of dyes by Ag NPs.

  20. Theoretical infrared and electronic absorption spectra of C16H10 isomers, their ions and doubly ions

    NASA Astrophysics Data System (ADS)

    Naganathappa, Mahadevappa; Chaudhari, Ajay

    2012-09-01

    Polycyclic aromatic hydrocarbons (PAHs) or PAH-related molecules are considered to be responsible for the unidentified infrared (UIR) emission features at 3.3, 6.2, 7.7, 8.6 and 11.2 μm. However, the exact identification of PAH or PAH-related molecules is difficult. There have been several investigations on the spectroscopic characterization of PAH molecules. But none of them compared the spectra of isomers of PAHs, which might have help in the identification of the UIR emission features. This work presents the infrared and electronic absorption spectra of isomers of C16H10. The aim of the present work is to compare infrared and electronic absorption spectra of four isomers of C16H10 PAH viz. pyrene, aceanthrylene, acephenanthrylene and fluoranthene, their ions and doubly ions. We also compare the spectra of pyrene in the gas-phase and in H2O ice. We have used the density functional theory with B3LYP exchange and correlation functional and 6-311++g** basis set to study the infrared spectra. The time-dependent density functional theory (TDDFT) has been used to obtain the electronic absorption spectra. Significant difference in the CC stretching, CH in-plane bending and CH out-of-plane bending vibration modes is observed for the isomers of C16H10 whereas there is no large difference in the CH stretching vibration band. A significant change in the vibrational band is observed for pyrene in H2O ice compared to gas-phase pyrene. Though isomers of C16H10 PAH have the same number of carbon and hydrogen atoms, their spectroscopic characteristics are different. This study should help in identifying the isomers of C16H10, their ions and doubly cation in the interstellar medium.

  1. Effects of alcohols on fluorescence intensity and color of a discharged-obelin-based biomarker.

    PubMed

    Alieva, Roza R; Belogurova, Nadezhda V; Petrova, Alena S; Kudryasheva, Nadezhda S

    2014-05-01

    Photoproteins are responsible for bioluminescence of marine coelenterates; bioluminescent and fluorescent biomarkers based on photoproteins are useful for monitoring of calcium-dependent processes in medical investigations. Here, we present the analysis of intensity and color of light-induced fluorescence of Ca(2+)-discharged photoprotein obelin in the presence of alcohols (ethanol and glycerol). Complex obelin spectra obtained at different concentrations of the alcohols at 350- and 280-nm excitation (corresponding to polypeptide-bound coelenteramide and tryptophan absorption regions) were deconvoluted into Gaussian components; fluorescent intensity and contributions of the components to experimental spectra were analyzed. Five Gaussian components were found in different spectral regions-ultraviolet (tryptophan emission), blue-green (coelenteramide emission), and red (hypothetical indole-coelenteramide exciplex emission). Inhibition coefficients and contributions of the components to experimental fluorescent spectra showed that presence of alcohols increased contributions of ultraviolet, violet, and red components, but decreased contributions of components in the blue-green region. The effects were related to (1) changes of proton transfer efficiency in fluorescent S*1 state of coelenteramide in the obelin active center and (2) formation of indole-coelenteramide exciplex at 280-nm photoexcitation. The data show that variation of fluorescence color and intensity in the presence of alcohols and dependence of emission spectra on excitation wavelength should be considered while applying the discharged obelin as a fluorescence biomarker.

  2. Potential benefits of triethylamine as n-electron donor in the estimation of forskolin by electronic absorption and emission spectroscopy.

    PubMed

    Raju, Gajula; Ram Reddy, A

    2016-02-05

    Diterpenoid forskolin was isolated from Coleus forskolii. The electronic absorption and emission studies of forskolin were investigated in various solvents with an aim to improve its detection limits. The two chromophores present in the diterpenoid are not conjugated leading to the poor absorption and emission of UV light. The absorption and fluorescence spectra were solvent specific. In the presence of a monodentate ligand, triethylamine the detection of forskolin is improved by 3.63 times in ethanol with the fluorescence method and 3.36 times in DMSO by the absorption spectral method. The longer wavelength absorption maximum is blue shifted while the lower energy fluorescence maximum is red shifted in the presence of triethylamine. From the wavelength of fluorescence maxima of the exciplex formed between excited forskolin and triethylamine it is concluded that the order of reactivity of hydroxyl groups in the excited state forskolin is in the reverse order to that of the order of the reactivity of hydroxyl groups in its ground state. Copyright © 2015. Published by Elsevier B.V.

  3. Fluorescence excitation-emission matrix spectroscopy of vitiligo skin in vivo (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Zhao, Jianhua; Richer, Vincent; Al Jasser, Mohammed; Zandi, Soodabeh; Kollias, Nikiforos; Kalia, Sunil; Zeng, Haishan; Lui, Harvey

    2016-02-01

    Fluorescence signals depend on the intensity of the exciting light, the absorption properties of the constituent molecules, and the efficiency with which the absorbed photons are converted to fluorescence emission. The optical features and appearance of vitiligo have been explained primarily on the basis of reduced epidermal pigmentation, which results in abnormal white patches on the skin. The objective of this study is to explore the fluorescence properties of vitiligo and its adjacent normal skin using fluorescence excitation-emission matrix (EEM) spectroscopy. Thirty five (35) volunteers with vitiligo were acquired using a double-grating spectrofluorometer with excitation and emission wavelengths of 260-450 nm and 300-700 nm respectively. As expected, the most pronounced difference between the spectra obtained from vitiligo lesions compared to normally pigmented skin was that the overall fluorescence was much higher in vitiligo; these differences increased at shorter wavelengths, thus matching the characteristic spectral absorption of epidermal melanin. When comparing the fluorescence spectra from vitiligo to normal skin we detected three distinct spectral bands centered at 280nm, 310nm, and 335nm. The 280nm band may possibly be related to inflammation, whereas the 335 nm band may arise from collagen or keratin cross links. The source of the 310 nm band is uncertain; it is interesting to note its proximity to the 311 nm UV lamps used for vitiligo phototherapy. These differences are accounted for not only by changes in epidermal pigment content, but also by other optically active cutaneous biomolecules.

  4. 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.

  5. 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.

  6. Infrared fluorescence from PAHs in the laboratory

    NASA Technical Reports Server (NTRS)

    Cherchneff, Isabelle; Barker, John R.

    1989-01-01

    Several celestial objects, including UV rich regions of planetary and reflection nebulae, stars, H II regions, and extragalactic sources, are characterized by the unidentified infrared emission bands (UIR bands). A few years ago, it was proposed that polycyclic aromatic hydrocarbon species (PAHs) are responsible for most of the UIR bands. This hypothesis is based on a spectrum analysis of the observed features. Comparisons of observed IR spectra with lab absorption spectra of PAHs support the PAH hypothesis. An example spectrum is represented, where the Orion Bar 3.3 micron spectrum is compared with the absorption frequencies of the PAHs Chrysene, Pyrene, and Coronene. The laser excited 3.3 micron emission spectrum is presented from a gas phase PAH (azulen). The infrared fluorescence theory (IRF) is briefly explained, followed by a description of the experimental apparatus, a report of the results, and discussion.

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

    PubMed

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

    2012-10-05

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

  8. Dual fluorescence of syringaldazine

    NASA Astrophysics Data System (ADS)

    Rajendiran, N.; Balasubramanian, T.

    2007-11-01

    The absorption and fluorescence spectra of syringaldazine (SYAZ) has been recorded in solvents of different polarity, pH and β-cyclodextrin (β-CD) and compared with syringaldehyde (SYAL). The inclusion complex of SYAZ with β-CD is investigated by UV-vis, fluorimetry, AM 1, FT-IR, 1H NMR and scanning electron microscope (SEM). Δ G value suggests the inclusion process is an exothermic and spontaneous. In all solvents a dual fluorescence is observed for SYAZ, whereas, SYAL shows a dual luminescence only in polar solvents. The excitation spectra for the 410 nm is different from 340 nm indicate two different species present in this molecule. In pH solutions: (i) a large red shifted maxima is observed in the dianion and is due to large interactions between the aromatic ring and (ii) the large blue shift at pH ˜4.5, is due to dissociation of azine group and formation of aldehyde. β-CD studies reveal that, SYAZ forms a 1:2 complex from 1:1 complex with β-CD.

  9. Synthesis and characterization of the fluorescent probes for the labeling of Microthrix parvicella.

    PubMed

    Li, Songya; Fei, Xuening; Jiao, Xiumei; Lin, Dayong; Zhang, Baolian; Cao, Lingyun

    2016-03-01

    Although the fluorescent in situ hybridization (FISH) has been widely used to identify the Microthrix parvicella (M. parvicella), there are a few disadvantages and difficulties, such as complicated process, time consuming, etc. In this work, a series of fluorescent probes, which were modified by long-chain alkane with hydrophobic property and based on the property of M. parvicella utilizing long-chain fatty acids (LCFA), for the labeling of M. parvicella in bulking sludge were designed, synthesized, and characterized. The probes were characterized by ultraviolet-visible (UV-Vis) absorption spectra, fluorescence spectra, (1)H NMR spectra, and mass spectra, and the photostability and hydrophobic property of probes were investigated. All the results showed that the probes were quite stable and suitable for the fluorescent labeling. The probes had a large stoke shift of 98-137 nm, which was benefit for the fluorescent labeling. In the fluorescent labeling of M. parvicella by the synthesized probes, the probes had excellent labeling effects. By comparison of the images and the Image Pro Plus 6.0 analysis, the optimal concentration of the probes in the activated sludge sample for labeling was 0.010 mmol/L and the probe 3d had the best labeling. In addition, the effect of the duration time of probes was also investigated, and the results showed that the fluorescent intensity of probes hardly changed in a long period of time and it was suitable for labeling.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Baishya, K.; Idrobo, J. C.; Ogut, S.

    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, yetmore » 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.« less

  11. [Chromophoric dissolved organic matter absorption characteristics with relation to fluorescence in typical macrophyte, algae lake zones of Lake Taihu].

    PubMed

    Zhang, Yun-lin; Qin, Bo-qiang; Ma, Rong-hua; Zhu, Guang-wei; Zhang, Lu; Chen, Wei-min

    2005-03-01

    Chromophoric dissolved organic matter (CDOM) represents one of the primary light-absorbing species in natural waters and plays a critical in determining the aquatic light field. CDOM shows a featureless absorption spectrum that increases exponentially with decreasing wavelength, which limits the penetration of biologically damaging UV-B radiation (wavelength from 280 to 320 nm) in the water column, thus shielding aquatic organisms. CDOM absorption measurements and their relationship with dissolved organic carbon (DOC), and fluorescence are presented in typical macrophyte and algae lake zone of Lake Taihu based on a field investigation in April in 2004 and lab analysis. Absorption spectral of CDOM was measured from 240 to 800 nm using a Shimadzu UV-2401PC UV-Vis recording spectrophotometer. Fluorescence with an excitation wavelength of 355 nm, an emission wavelength of 450 nm is measured using a Shimadzu 5301 spectrofluorometer. Concentrations of DOC ranged from 6.3 to 17.2 mg/L with an average of 9.08 +/- 2.66 mg/L. CDOM absorption coefficients at 280 nm and 355 nm were in the range of 11.2 - 32.6 m(-1) (average 17.46m(-1) +/- 5.75 m(-1) and 2.4 - 8.3 m(-1) (average 4.17m(-1) +/- 1.47 m(-l)), respectively. The values of the DOC-specific absorption coefficient at 355 nm ranged from 0.31 to 0.64 L x (mg x m)-1. Fluorescence emission at 450 nm, excited at 355 nm, had a mean value of 1.32nm(-1) +/- 0.84 nm(-1). A significant lake zone difference is found in DOC concentration, CDOM absorption coefficient and fluorescence, but not in DOC-specific absorption coefficient and spectral slope coefficient. This regional distribution pattern is in agreement with the location of sources of yellow substance: highest concentrations close to river mouth under the influence of river inflow, lower values in East Lake Taihu. The values of algae lake zone are obvious larger than those of macrophyte lake zone. In Meiliang Bay, CDOM absorption, DOC concentration and fluorescence tend to

  12. Fluorescence emission of disperse Red 1 in solution at room temperature.

    PubMed

    Toro, Carlos; Thibert, Arthur; De Boni, Leonardo; Masunov, Artëm E; Hernández, Florencio E

    2008-01-24

    In this article, we report the fluorescence emission of Disperse Red 1 in solution at room temperature and pumping at 532 nm with a 25 mW diode laser. We have measured its fluorescence quantum yield in methanol, ethylene glycol, glycerol, and phenol obtaining values as high as 10(-3) in the aliphatic alcohols. The excitation spectra of Disperse Red 1 in all four solvents as well as its excitation anisotropy in glycerol are presented. Applying a Gaussian decomposition method to the absorption spectra along with the support from the excitation spectra, the positions of the different transitions in this pseudo-stilbene azobenzene dye were determined. Solvatochromic and isomerization constraint effects are discussed. Calculations using density functional theory at TD-B3LYP/6-31G*//HF/6-31G* level were performed to interpret the experimental observations.

  13. Fluorescence and absorption spectroscopy for warm dense matter studies and ICF plasma diagnostics

    NASA Astrophysics Data System (ADS)

    Hansen, S. B.; Harding, E. C.; Knapp, P. F.; Gomez, M. R.; Nagayama, T.; Bailey, J. E.

    2018-05-01

    The burning core of an inertial confinement fusion (ICF) plasma produces bright x-rays at stagnation that can directly diagnose core conditions essential for comparison to simulations and understanding fusion yields. These x-rays also backlight the surrounding shell of warm, dense matter, whose properties are critical to understanding the efficacy of the inertial confinement and global morphology. We show that the absorption and fluorescence spectra of mid-Z impurities or dopants in the warm dense shell can reveal the optical depth, temperature, and density of the shell and help constrain models of warm, dense matter. This is illustrated by the example of a high-resolution spectrum collected from an ICF plasma with a beryllium shell containing native iron impurities. Analysis of the iron K-edge provides model-independent diagnostics of the shell density (2.3 × 1024 e/cm3) and temperature (10 eV), while a 12-eV red shift in Kβ and 5-eV blue shift in the K-edge discriminate among models of warm dense matter: Both shifts are well described by a self-consistent field model based on density functional theory but are not fully consistent with isolated-atom models using ad-hoc density effects.

  14. Fluorescence and absorption spectroscopy for warm dense matter studies and ICF plasma diagnostics

    DOE PAGES

    Hansen, Stephanie B.; Harding, Eric C.; Knapp, Patrick F.; ...

    2018-03-07

    The burning core of an inertial confinement fusion (ICF) plasma produces bright x-rays at stagnation that can directly diagnose core conditions essential for comparison to simulations and understanding fusion yields. These x-rays also backlight the surrounding shell of warm, dense matter, whose properties are critical to understanding the efficacy of the inertial confinement and global morphology. In this work, we show that the absorption and fluorescence spectra of mid-Z impurities or dopants in the warm dense shell can reveal the optical depth, temperature, and density of the shell and help constrain models of warm, dense matter. This is illustrated bymore » the example of a high-resolution spectrum collected from an ICF plasma with a beryllium shell containing native iron impurities. Lastly, analysis of the iron K-edge provides model-independent diagnostics of the shell density (2.3 × 10 24 e/cm 3) and temperature (10 eV), while a 12-eV red shift in Kβ and 5-eV blue shift in the K-edge discriminate among models of warm dense matter: Both shifts are well described by a self-consistent field model based on density functional theory but are not fully consistent with isolated-atom models using ad-hoc density effects.« less

  15. Fluorescence properties of Yb3+-Er3+ co-doped phosphate glasses containing silver nanoparticles

    NASA Astrophysics Data System (ADS)

    Martínez Gámez, Ma A.; Vallejo H, Miguel A.; Kiryanov, A. V.; Licea-Jiménez, L.; Lucio M, J. L.; Pérez-García, S. A.

    2018-04-01

    Er3+-Yb3+ co-doped phosphate glasses containing silver nitrate (SN), were fabricated. Transmission electron microscopy (TEM) and x-ray photoelectron spectroscopy (XPS) analyses were used to evidence the nucleation and presence of silver nanoparticles (SNP). The basic parameters of the glasses were inspected by means of absorption and fluorescence spectra, and fluorescence lifetimes under excitation at 916 nm (in-band of Yb3+), and at 406 nm (in-band of surface plasmon resonance given by the presence of SNP). The spectra as well as estimates for the basic parameters defining the lasing/amplifying potential of the glasses were studied as a function of SN concentration. The experimental results indicate that by increasing the SN content an enhancement of Er3+/Yb3+ fluorescence takes place.

  16. Spectroscopic studies, fluorescence quenching by molecular oxygen and amplified spontaneous emission of 1,4-bis [2-(2-pyridyl) vinyl] benzene (P2VB) diolefinic laser dye

    NASA Astrophysics Data System (ADS)

    El-Daly, Samy A.; Ebeid, E. M.

    2014-04-01

    The UV-visible electronic absorption spectra, molar absorptivity, fluorescence spectra, fluorescence quantum yield and excited state lifetime of 1,4-bis [2-(2-pyridyl) vinyl] benzene P2VB were measured in different solvents. The fluorescence quenching of P2VB by molecular oxygen was also studied using lifetime measurements. A 2 × 10-4 mol dm-3 solution of P2VB in dimethyl formamide (DMF) gave amplified spontaneous emission (ASE) in blue spectral region with emission maximum at 420 nm upon pumping by 337.1 nitrogen laser pulse. The photochemical quantum yields (ϕc) of trans-cis photoisomerization of P2VB were calculated in different organic solvents. The photoreactivity of P2VB are also studied PMMA matrix.

  17. Total absorption spectroscopy of fission fragments relevant for reactor antineutrino spectra

    DOE PAGES

    Fallot, M.; Porta, A.; Meur, L. Le; ...

    2017-09-13

    Here, the accurate determination of reactor antineutrino spectra remains a very active research topic for which new methods of study have emerged in recent years. Indeed, following the long-recognized reactor anomaly (measured antineutrino deficit in short baseline reactor experiments when compared with spectral predictions), the three international reactor neutrino experiments Double Chooz, Daya Bay and Reno have recently demonstrated the existence of spectral distortions in their measurements with respect to the same predictions. These spectral predictions were obtained through the conversion of integral beta-energy spectra obtained at the ILL research reactor. Several studies have shown that the underlying nuclear physicsmore » required for the conversion of these spectra into antineutrino spectra is not totally understood. An alternative to such converted spectra is a complementary approach that consists of determining the antineutrino spectrum by means of the measurement and processing of nuclear data. The beta properties of some key fission products suffer from the pandemonium effect which can be circumvented by the use of the Total Absorption Gamma-ray Spectroscopy technique (TAGS). The two main contributors to the Pressurized Water Reactor antineutrino spectrum in the region where the spectral distortion has been observed are 92Rb and 142Cs, which have been measured at the radioactive beam facility of the University of Jyvaskyla in two TAGS experiments. We present the results of the analysis of the TAGS measurements of the β-decay properties of 92Rb along with preliminary results on 142Cs and report on the measurements already performed.« less

  18. Total absorption spectroscopy of fission fragments relevant for reactor antineutrino spectra

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Fallot, M.; Porta, A.; Meur, L. Le

    Here, the accurate determination of reactor antineutrino spectra remains a very active research topic for which new methods of study have emerged in recent years. Indeed, following the long-recognized reactor anomaly (measured antineutrino deficit in short baseline reactor experiments when compared with spectral predictions), the three international reactor neutrino experiments Double Chooz, Daya Bay and Reno have recently demonstrated the existence of spectral distortions in their measurements with respect to the same predictions. These spectral predictions were obtained through the conversion of integral beta-energy spectra obtained at the ILL research reactor. Several studies have shown that the underlying nuclear physicsmore » required for the conversion of these spectra into antineutrino spectra is not totally understood. An alternative to such converted spectra is a complementary approach that consists of determining the antineutrino spectrum by means of the measurement and processing of nuclear data. The beta properties of some key fission products suffer from the pandemonium effect which can be circumvented by the use of the Total Absorption Gamma-ray Spectroscopy technique (TAGS). The two main contributors to the Pressurized Water Reactor antineutrino spectrum in the region where the spectral distortion has been observed are 92Rb and 142Cs, which have been measured at the radioactive beam facility of the University of Jyvaskyla in two TAGS experiments. We present the results of the analysis of the TAGS measurements of the β-decay properties of 92Rb along with preliminary results on 142Cs and report on the measurements already performed.« less

  19. 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.

  20. 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.

  1. 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.

  2. Development of a Time Domain Fluorimeter for Fluorescent Lifetime Multiplexing Analysis

    PubMed Central

    Weissleder, Ralph; Mahmood, Umar

    2009-01-01

    We show that a portable, inexpensive USB-powered time domain fluorimeter (TDF) and analysis scheme were developed for use in evaluating a new class of fluorescent lifetime multiplexed dyes. Fluorescent proteins, organic dyes, and quantum dots allow the labeling of more and more individual features within biological systems, but the wide absorption and emission spectra of these fluorophores limit the number of distinct processes which may be simultaneously imaged using spectral separation alone. By additionally separating reporters in a second dimension, fluorescent lifetime multiplexing provides a means to multiply the number of available imaging channels. PMID:19830273

  3. Comparative study on fluorescence spectra of Chinese medicine north and south isatis root granules

    NASA Astrophysics Data System (ADS)

    Liang, Lan; He, Qing; Chen, Zhenqiang; Zhu, Siqi

    2016-03-01

    Since the spectral imaging technology emerged, it has gained a lot of application achievements in the military field, precision agriculture and biomedical science. When the fluorescence spectrum imaging first applied to the detection of the feature resource of Chinese herbal medicine, the characteristics of holistic and ambiguity made it a new approach to the traditional Chinese medicine testing. In this paper, we applied this method to study the Chinese medicine north and south isatis root granules by comparing their fluorescence spectra. Using cluster analysis, the results showed that the north and south Banlangen can not be divided by ascription. And these indicate that there is a large difference in the quality of Banlangen granules on the market, and fluorescence spectrum imaging method can be used in monitoring the quality of radix isatidis granules.

  4. [Absorption and fluorescence characteristics of dissolved organic matter (DOM) in rainwater and sources analysis in summer and winter season].

    PubMed

    Liang, Jian; Jiang, Tao; WeiI, Shi-Qiang; Lu, Song; Yan, Jin-Long; Wang, Qi-Lei; Gao, Jie

    2015-03-01

    This study aimed at evaluating the variability of the optical properties including UV-Vis and fluorescence characteristics of dissolved organic matter (DOM) from rainwater in summer and winter seasons. UV-Vis and fluorescence spectroscopy, together with Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) model and fire events map, were conducted to characterize DOM and investigate its sources and contributions. The results showed that as compared with aquatic and soil DOM, rainwater DOM showed similar spectral characteristics, suggesting DOM in precipitation was also an important contributor to DOM pool in terrestrial and aquatic systems. The concentrations of DOC in rainwater were 0.88-12.80 mg x L(-1), and the CDOM concentrations were 3.17-21.11 mg x L(-1). Differences of DOM samples between summer and winter were significant (P < 0.05). In comparison to summer, DOM samples in winter had lower molecular weight and aromaticity, and also lower humification. Input of DOM in winter was predominantly derived from local and short-distance distances, while non-special scattering sources were identified as the main contributors in summer. Although absorption and fluorescence spectroscopy could be used to identify DOM composition and sources, there were obvious differences in spectra and sources analysis between rainwater DOM and the others from other sources. Thus, the classic differentiation method by "allochthonous (terrigenous) and autochthonous (authigenic)" is possibly too simple and arbitrary for characterization of DOM in rainwater.

  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. Liquid helium cryostat with internal fluorescence detection for x-ray absorption studies in the 2-6 keV energy region

    NASA Astrophysics Data System (ADS)

    McFarlane Holman, Karen L.; Latimer, Matthew J.; Yachandra, Vittal K.

    2004-06-01

    X-ray absorption spectroscopy (XAS) in the intermediate x-ray region (2-6 keV) for dilute biological samples has been limited because of detector/flux limitations and inadequate cryogenic instrumentation. We have designed and constructed a new tailpiece/sample chamber for a commercially available liquid helium cooled cryostat which overcomes difficulties related to low fluorescence signals by using thin window materials and incorporating an internal photodiode detector. With the apparatus, XAS data at the Cl, S, and Ca K edges have been collected on frozen solutions and biological samples at temperatures down to 60 K. A separate chamber has been incorporated for collecting room-temperature spectra of standard compounds (for energy calibration purposes) which prevents contamination of the cryostat chamber and allows the sample to remain undisturbed, both important concerns for studying dilute and radiation-sensitive samples.

  7. Exciton-Dominated Core-Level Absorption Spectra of Hybrid Organic-Inorganic Lead Halide Perovskites.

    PubMed

    Vorwerk, Christian; Hartmann, Claudia; Cocchi, Caterina; Sadoughi, Golnaz; Habisreutinger, Severin N; Félix, Roberto; Wilks, Regan G; Snaith, Henry J; Bär, Marcus; Draxl, Claudia

    2018-04-19

    In a combined theoretical and experimental work, we investigate X-ray absorption near-edge structure spectroscopy of the I L 3 and the Pb M 5 edges of the methylammonium lead iodide (MAPbI 3 ) hybrid inorganic-organic perovskite and its binary phase PbI 2 . The absorption onsets are dominated by bound excitons with sizable binding energies of a few hundred millielectronvolts and pronounced anisotropy. The spectra of both materials exhibit remarkable similarities, suggesting that the fingerprints of core excitations in MAPbI 3 are essentially given by its inorganic component, with negligible influence from the organic groups. The theoretical analysis complementing experimental observations provides the conceptual insights required for a full characterization of this complex material.

  8. Electronic absorption spectra of chromium-bearing sapphirine

    NASA Astrophysics Data System (ADS)

    Langer, K.; Platonov, A. N.; Matsuk, S. S.; Andrut, M.

    1994-05-01

    Violet, non-pleochroic and greenish-blue, pleochroic chromium-substituted sapphirines were found in corundum-bearing spinel-websterite xenolites from the Yakutian kimberlite pipes Noyabrskaya (N) and Sludyanka (Sl), respectively. The crystallochemical formulae of sapphirine crystals from such xenolites were determined by EMP to be (Mg3.40Fe0.23Al3.25Cr0.16)[6] Al{1.00/[6]}[O2/Al4.53Si1.47O18] (N) and (Mg2.53Fe0.55 Mn0.04Ti{0.03/4+}Al3.55Cr{0.08/3+})[6]Al{1.00/[16]}[O2/Al4.28Si1.73O18] (Sl). Single crystal spectra in the range 35000 6000 cm1- showed a slightly polarization dependent absorption edge near 3200 cm1- (N) or 30000 cm1- (Sl) and unpolarized bands at 25300 and 17300 cm1-, typical of spin-allowed transitions, derived from 4A2g→4T1g and 4A2g→4T2g, of Cr3+ in octahedral sites, with point symmetry C1, of the structure. Another weak band at 23000 cm-1 in the sapphirine-N spectra is attributed to low symmetry splitting of the excited 4T1 (F)-State of Cr3+. These assignments lead to crystal field parameters Dq=1730cm-1 and B= 685cm-1 of Cr3+ in sapphirine. Crystallochemical and spectroscopic arguments suggest that Cr3+ subsitutes for Al in the M(1) or M(8) sites of the sapphirine structure. In addition to Cr3+-transitions, spectra of Sl exhibit weak dd-bands of Fe2+ at 10000 and 7700 cm1-, which are unpolarized in consistency with the C1 site symmetry of the octahedra in the structure. Spectra of Sl show also prominent, broad bands (Δv1/2˜-5000 cm1-) at 15000 and 11000 cm1-, which occur in E//Y(//b) and E//Z(//c=12°) only and exhibit an intensity ratio αY∶αz close to 1∶3. This result, the large half width, as well as band energy — MM distance considerations suggest that these bands originate from Fe2+[6]-Fe3+[6] charge-transfer transitions in wall octahedra M(1)M(2), M(6)M(7) etc., forming MM vectors of 30° with the c-axis. The lack of Fe2+-Fe3+ charge-transfer bands in sapphirine N might indicate a lower oxygen fugacity during the formation of

  9. [Two-photon up-conversion fluorescence of a neodymium organic framework Nd(BTC)].

    PubMed

    Xu, Hui; Jin, Run-zhi; Wu, Chun-yang; Yang, Yu; Qian, Guo-dong

    2008-08-01

    In the present work, a neodymium organic framework Nd(BTC) was synthesized by the solvothermal reaction of Nd(NO3)3 x 5H2O and H3BTC (BTC = 1,3,5-benzenetricarboxylate) in mixed solvents of DMF, ethanol and water, and was identified by elemental analysis. This MOF complex was characterized using X-ray diffraction (XRD), thermogravimetry-differential scanning calorimetry (TGA-DSC) analysis, UV-visible absorption spectra and fluorescence spectra. This polycrystalline powder lost DMF and H2O when heated to 120 degrees C, then remained stable till the temperature reached 500 degrees C. Near infrared fluorescence at 1064 nm due to the 4 F3/2--> 4 I11/2 transition of Nd3+ ions was exhibited when excited by 808 nm laser beam. It was also been found that up-conversion fluorescence of Nd(BTC) peaked at about 450 nm due to 2 D5/2 -->4 I11/2 transition of Nd3+ ions can be observed under the excitation of a 580 nm laser line. The mechanism of the up-conversion fluorescence of Nd(BTC) at around 450 nm under the excitation of 580 nm laser can be ascribed to both excited-state absorption and energy transfer up-conversion. This result indicated that such MOF can be employed as an up-conversion luminescence material in many potential application areas such as bio-labeling and fluorescence image.

  10. Solvent induced fluorescence enhancement of graphene oxide studied by ultrafast spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhao, Litao; Chen, Jinquan; He, Xiaoxiao; Yu, Xiantong; Yan, Shujun; Zhang, Sanjun; Pan, Haifeng; Xu, Jianhua

    2018-05-01

    Femtosecond transient absorption (TA) spectroscopy combined with picosecond time resolved fluorescence (TRF) were used to reveal the fluorescence kinetics of graphene oxide (GO) in water, ethanol and water-ethanol mixtures. Size-independent fluorescence of GO were observed in water, and pH-dependent fluorescence spectra could be fitted well by a triple emission relaxation with peaks around 440 nm, 500 nm, and 590 nm respectively. The results indicate that polycyclic aromatic hydrocarbons (PAHs) linked by oxygen-containing functional groups dominate GO's fluorescence emission. GO's fluorescence quantum yield was measured to be 2.8% in ethanol but 1.2% in water. The three decay components fluorescence decay, as well as the transient absorption dynamics with an offset, confirmed this solvent induced fluorescence enhancement. GO's Raman spectral signals showed that GO in ethanol has a smaller average size of PAHs than that of GO in water. Therefore, besides other enhancement effects reported in literatures, we proposed that solvents could also change the size of PAHs, resulting in a photoluminescence enhancement. Our experimental data demonstrates that GO's quantum yield could be up to 2.8% in water and 8.4% in ethanol and this observation may help ones to improve GO's photoluminescence efficiency as well as its applications in solution.

  11. X-Ray Absorption Spectra of Amorphous Ices from GW Quasiparticle Calculation

    NASA Astrophysics Data System (ADS)

    Kong, Lingzhu; Car, Roberto

    2013-03-01

    We use a GW approach[2] to compute the x-ray absorption spectra of model low- and high-density amorphous ice structures(LDA and HDA)[3]. We include the structural effects of quantum zero point motion using colored-noise Langevin molecular dynamics[4]. The calculated spectra differences in the main and post edge region between LDA and HDA agree well with experimental observations. We attribute these differences to the presence of interstitial molecules within the first coordination shell range in HDA. This assignment is further supported by a calculation of the spectrum of ice VIII, a high-pressure structure that maximizes the number of interstitial molecules and, accordingly, shows a much weaker post-edge feature. We further rationalize the spectral similarity between HDA and liquid water, and between LDA and ice Ih in terms of the respective similarities in the H-bond network topology and bond angle distributions. Supported by grants DOE-DE-SC0005180, DOE DE-SC0008626 and NSF-CHE-0956500.

  12. The effect of nonlocal dielectric response on the surface-enhanced Raman and fluorescence spectra of molecular systems

    NASA Astrophysics Data System (ADS)

    Wei, Yong; Pei, Huan; Li, Li; Zhu, Yanying

    2018-06-01

    We present a theoretical study on the influence of the nonlocal dielectric response on surface-enhanced resonant Raman scattering (SERRS) and fluorescence (SEF) spectra of a model molecule confined in the center of a Ag nanoparticle (NP) dimer. In the simulations, the nonlocal dielectric response caused by the electron–hole pair generation in Ag NPs was computed with the d-parameter theory, and the scattering spectra of a model molecule representing the commonly used fluorescent dye rhodamine 6G (R6G) were obtained by density-matrix calculations. The influence of the separation between Ag NP dimers on the damping rate and scattering spectra with and without the nonlocal response were systematically analyzed. The results show that the nonlocal dielectric response is very sensitive to the gap distance of the NP dimers, and it undergoes much faster decay with the increase of the separation than the radiative and energy transfer rates. The Raman and fluorescence peaks as simulated with the nonlocal dielectric response are relative weaker than that without the nonlocal effect for smaller NP separations because the extra decay rates of the nonlocal effect could reduce both the population of the excited state and the interband coherence between the ground and excited states. Our result also indicates that the nonlocal effect is more prominent on the SEF process than the SERRS process.

  13. The effect of nonlocal dielectric response on the surface-enhanced Raman and fluorescence spectra of molecular systems.

    PubMed

    Wei, Yong; Pei, Huan; Li, Li; Zhu, Yanying

    2018-05-04

    We present a theoretical study on the influence of the nonlocal dielectric response on surface-enhanced resonant Raman scattering (SERRS) and fluorescence (SEF) spectra of a model molecule confined in the center of a Ag nanoparticle (NP) dimer. In the simulations, the nonlocal dielectric response caused by the electron-hole pair generation in Ag NPs was computed with the d-parameter theory, and the scattering spectra of a model molecule representing the commonly used fluorescent dye rhodamine 6G (R6G) were obtained by density-matrix calculations. The influence of the separation between Ag NP dimers on the damping rate and scattering spectra with and without the nonlocal response were systematically analyzed. The results show that the nonlocal dielectric response is very sensitive to the gap distance of the NP dimers, and it undergoes much faster decay with the increase of the separation than the radiative and energy transfer rates. The Raman and fluorescence peaks as simulated with the nonlocal dielectric response are relative weaker than that without the nonlocal effect for smaller NP separations because the extra decay rates of the nonlocal effect could reduce both the population of the excited state and the interband coherence between the ground and excited states. Our result also indicates that the nonlocal effect is more prominent on the SEF process than the SERRS process.

  14. Tuning optical and three photon absorption properties in graphene oxide-polyvinyl alcohol free standing films

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Karthikeyan, B., E-mail: bkarthik@nitt.edu; Hariharan, S.; Udayabhaskar, R.

    2016-07-11

    We report the optical and nonlinear optical properties of graphene oxide (GO)-polyvinyl alcohol (PVA) free standing films. The composite polymer films were prepared in ex-situ method. The variation in optical absorption spectra and optical constants with the amount of GO loading was noteworthy from the optical absorption spectroscopic studies. Nonlinear optical studies done at 532 nm using 5 ns laser pulses show three photon absorption like behaviour. Both steady state and time resolved fluorescence studies reveal that the GO was functioning as a pathway for the decay of fluorescence from PVA. This is attributed to the energy level modifications of GO throughmore » hydroxyl groups with PVA. Raman spectroscopy also supports the interaction between GO and PVA ions through OH radicals.« less

  15. Determination of absorption coefficient of nanofluids with unknown refractive index from reflection and transmission spectra

    NASA Astrophysics Data System (ADS)

    Kim, Joong Bae; Lee, Seungyoon; Lee, Kyungeun; Lee, Ikjin; Lee, Bong Jae

    2018-07-01

    It has been shown that the absorption coefficient of a nanofluid can be actively tuned by changing material, size, shape, and concentration of the nanoparticle suspension. In applications of engineered nanofluids for the direct absorption of solar radiation, it is important to experimentally characterize the absorption coefficient of nanofluids in the solar spectrum. If the refractive index of the base fluid (i.e., the solution without nanoparticles) is known a priori, the absorption coefficient of nanofluids can be easily determined from the transmission spectrum. However, if the refractive index of the base fluid is not known, it is not straightforward to extract the absorption coefficient solely from the transmission spectrum. The present work aims to develop an analytical method of determining the absorption coefficient of nanofluids with unknown refractive index by measuring both reflection and transmission spectra. The proposed method will be validated with deionized water, and the effect of measurement uncertainty will be carefully examined. Finally, the general applicability of the proposed method will also be demonstrated for Therminol VP-1 as well as the Therminol VP-1 - graphite nanofluid.

  16. Anomalous fluorescence enhancement and fluorescence quenching of graphene quantum dots by single walled carbon nanotubes.

    PubMed

    Das, Ruma; Rajender, Gone; Giri, P K

    2018-02-07

    We explore the mechanism of the fluorescence enhancement and fluorescence quenching effect of single walled carbon nanotubes (SWCNTs) on highly fluorescent graphene quantum dots (GQDs) over a wide range of concentrations of SWCNTs. At very low concentrations of SWCNTs, the fluorescence intensity of the GQDs is enhanced, while at higher concentrations, systematic quenching of fluorescence is observed. The nature of the Stern-Volmer plot for the latter case was found to be non-linear indicating a combined effect of dynamic and static quenching. The contribution of the dynamic quenching component was assessed through the fluorescence lifetime measurements. The contribution of static quenching is confirmed from the red shift of the fluorescence spectra of the GQDs after addition of SWCNTs. The fluorescence intensity is first enhanced at very low concentration due to improved dispersion and higher absorption by GQDs, while at higher concentration, the fluorescence of GQDs is quenched due to the complex formation and associated reduction of the radiative sites of the GQDs, which is confirmed from time-resolved fluorescence measurements. Laser confocal microscopy imaging provides direct evidence of the enhancement and quenching of fluorescence at low and high concentrations of SWCNTs, respectively. This study provides an important insight into tuning the fluorescence of GQDs and understanding the interaction between GQDs and different CNTs, which is important for bio-imaging and drug delivery applications.

  17. Retrieval of phytoplankton cell size from chlorophyll a specific absorption and scattering spectra of phytoplankton.

    PubMed

    Zhou, Wen; Wang, Guifen; Li, Cai; Xu, Zhantang; Cao, Wenxi; Shen, Fang

    2017-10-20

    Phytoplankton cell size is an important property that affects diverse ecological and biogeochemical processes, and analysis of the absorption and scattering spectra of phytoplankton can provide important information about phytoplankton size. In this study, an inversion method for extracting quantitative phytoplankton cell size data from these spectra was developed. This inversion method requires two inputs: chlorophyll a specific absorption and scattering spectra of phytoplankton. The average equivalent-volume spherical diameter (ESD v ) was calculated as the single size approximation for the log-normal particle size distribution (PSD) of the algal suspension. The performance of this method for retrieving cell size was assessed using the datasets from cultures of 12 phytoplankton species. The estimations of a(λ) and b(λ) for the phytoplankton population using ESD v had mean error values of 5.8%-6.9% and 7.0%-10.6%, respectively, compared to the a(λ) and b(λ) for the phytoplankton populations using the log-normal PSD. The estimated values of C i ESD v were in good agreement with the measurements, with r 2 =0.88 and relative root mean square error (NRMSE)=25.3%, and relatively good performances were also found for the retrieval of ESD v with r 2 =0.78 and NRMSE=23.9%.

  18. Effect of silver nanoparticles on the fluorescence of Pb2+ and compositional dependence of Sm3+ fluorescence in borate glasses

    NASA Astrophysics Data System (ADS)

    Olumoroti, Akinloluwa T.

    Borate glasses have been widely studied due to their good optical and mechanical properties. Lead and bismuth (PbO/Bi2O 3:B2O3) borate glasses belong to a family of heavy metal oxide (HMO) glasses which are well known to be chemically durable, stable against atmospheric moisture, have low melting temperatures and good corrosion resistance. The first part of this work deals with lead borate glasses with silver nanoparticles (NPs) introduced into the glass matrix. Transmission electron microscopy characterization is done to verify the nucleation of NPs. Fluorescence and optical absorption experiments are then carried out after different heat treatment duration to investigate the influence of silver NPs on the optical properties of lead (Pb2+) by comparing with a glass sample without silver NPs. Optical absorption experiments show that a well-defined surface plasmon resonance (SPR) peak due to Ag NPs can be observed only for samples that were annealed for 36 hrs. Pb2+ fluorescence spectra reveal that the presence of silver NPs creates new emission centers for Pb2+ ions by altering their chemical environment. The second part of the work involves the use of samarium (a rare earth ion) as a dopant in lead and bismuth borate glasses. The concentration of samarium (Sm3+) is fixed and the base glass composition is varied. The goal is to investigate the compositional dependence of optical properties of samarium in the base glass (PbO/Bi2O3:B 2O3). Optical absorption spectra have been collected and the oscillator strength of each transition - including the hypersensitive - is obtained. The Optical absorption edge is found to shift toward lower energies with increasing PbO/Bi2O3 concentration. Both the oscillator strength and the peak position of the hypersensitive transition show significant variation with glass composition. Strong interaction between Sm3+ ions and Pb2+/Bi3+ ions can also be seen from the variations in the fluorescence emission properties of Sm3+ as a

  19. 5-ALA/PpIX fluorescence detection of gastrointestinal neoplasia

    NASA Astrophysics Data System (ADS)

    Borisova, Ekaterina G.; Vladimirov, Borislav; Terziev, Ivan; Ivanova, Radina; Avramov, Latchezar

    2009-07-01

    In the recent study delta-ALA/PpIX is used as fluorescent marker for dysplasia and tumor detection in esophagus, stomach and colon. ALA is administered per os six to eight (depending on the lesion location) hours before measurements at dose 20mg/kg weight. High-power light-emitting diode at 405 nm is used as an excitation source. Special opto-mechanical device is built for the LED to use the light guide of standard video-endoscopic system. Through endoscopic instrumental channel a fiber is applied to return information about fluorescence to microspectrometer. The fluorescence detected from tumor sites has very complex spectral origins. It consists of autofluorescence, fluorescence from exogenous fluorophores and re-absorption from the chromophores accumulated in the tissue investigated. Spectral features observed during endoscopic investigations could be distinct as the next regions: 450-630 nm region, where tissue autofluorescence is observed; 630-710 nm region, where fluorescence of PpIX is clearly pronounced; 530-580 nm region, where minima in the autofluorescence signal are observed, related to re-absorption of oxy-hemoglobin in this spectral area. Endogenous and exogenous fluorescence spectra are used to develop simple but effective algorithm, based on dimensionless ratio of the signals at 560 and 635 nm, for differentiation of normal/abnormal gastrointestinal tissues. Very good correlation between fluorescence signals and histology examination of the lesions investigated is achieved.

  20. 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.

  1. Electronic structures and spectra of two antioxidants: uric acid and ascorbic acid

    NASA Astrophysics Data System (ADS)

    Shukla, M. K.; Mishra, P. C.

    1996-04-01

    Electronic absorption and fluorescence spectra of aqueous solutions of two well known antioxidants, uric acid and ascorbic acid (vitamin C), have been studied at different pH. The observed spectra have been interpreted in terms of neutral and anionic forms of the molecules with the help of molecular orbital calculations. The N 3 site of uric acid has been shown to be the most acidic. Fluorescence of uric acid seems to originate from an anion of the molecule in a wide pH range. Around pH 3, both the neutral and anionic forms of ascorbic acid appear to be present in aqueous solutions. In aqueous media, ascorbic acid appears to get converted easily to its dehydro form and this conversion does not seem to be reversible. An anion of dehydroascorbic acid seems to be formed on heating dehydroascorbic acid in aqueous solutions.

  2. Exciton-Dominated Core-Level Absorption Spectra of Hybrid Organic–Inorganic Lead Halide Perovskites

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Vorwerk, Christian; Hartmann, Claudia; Cocchi, Caterina

    In a combined theoretical and experimental work, we investigate X-ray absorption near-edge structure spectroscopy of the I L 3 and the Pb M 5 edges of the methylammonium lead iodide (MAPbI 3) hybrid inorganic-organic perovskite and its binary phase PbI 2. The absorption onsets are dominated by bound excitons with sizable binding energies of a few hundred millielectronvolts and pronounced anisotropy. The spectra of both materials exhibit remarkable similarities, suggesting that the fingerprints of core excitations in MAPbI 3 are essentially given by its inorganic component, with negligible influence from the organic groups. Furthermore, the theoretical analysis complementing experimental observationsmore » provides the conceptual insights required for a full characterization of this complex material.« less

  3. Exciton-Dominated Core-Level Absorption Spectra of Hybrid Organic–Inorganic Lead Halide Perovskites

    DOE PAGES

    Vorwerk, Christian; Hartmann, Claudia; Cocchi, Caterina; ...

    2018-03-23

    In a combined theoretical and experimental work, we investigate X-ray absorption near-edge structure spectroscopy of the I L 3 and the Pb M 5 edges of the methylammonium lead iodide (MAPbI 3) hybrid inorganic-organic perovskite and its binary phase PbI 2. The absorption onsets are dominated by bound excitons with sizable binding energies of a few hundred millielectronvolts and pronounced anisotropy. The spectra of both materials exhibit remarkable similarities, suggesting that the fingerprints of core excitations in MAPbI 3 are essentially given by its inorganic component, with negligible influence from the organic groups. Furthermore, the theoretical analysis complementing experimental observationsmore » provides the conceptual insights required for a full characterization of this complex material.« less

  4. Interactions of hemin with bovine serum albumin and human hemoglobin: A fluorescence quenching study

    NASA Astrophysics Data System (ADS)

    Makarska-Bialokoz, Magdalena

    2018-03-01

    The binding interactions between hemin (Hmi) and bovine serum albumin (BSA) or human hemoglobin (HHb), respectively, have been examined in aqueous solution at pH = 7.4, applying UV-vis absorption, as well as steady-state, synchronous and three-dimensional fluorescence spectra techniques. Representative results received for both BSA and HHb intrinsic fluorescence proceeding from the interactions with hemin suggest the formation of stacking non-covalent and non-fluorescent complexes in both the Hmi-BSA and Hmi-HHb systems, with highly possible concurrent formation of a coordinate bond between a group on the protein surface and the metal in Hmi molecule. All the values of calculated parameters, the binding, fluorescence quenching and bimolecular quenching rate constants point to the involvement of static quenching in both the systems studied. The blue shift in the synchronous fluorescence spectra imply the participation of both tryptophan and tyrosine residues in quenching of BSA and HHb intrinsic fluorescence. Depicted outcomes suggest that hemin is supposedly able to influence the physiological functions of BSA and HHb, the most important blood proteins, particularly in case of its overuse.

  5. Iron lines in model disk spectra of Galactic black hole binaries

    NASA Astrophysics Data System (ADS)

    Różańska, A.; Madej, J.; Konorski, P.; SaḐowski, A.

    2011-03-01

    Context. We present angle-dependent, broad-band intensity spectra from accretion disks around black holes of 10 M⊙. In our computations disks are assumed to be slim, which means that the radial advection is taken into account while computing the effective temperature of the disk. Aims: We attempt to reconstruct continuum and line spectra of X-ray binaries in soft state, i.e. dominated by the disk component of multitemperature shape. We follow how the iron-line complex depends on the external irradiation, an accretion rate, and a black hole spin. Methods: Full radiative transfer is solved including effects of Compton scattering, free-free and all important bound-free transitions of 10 main elements. We assume the LTE equation of state. Moreover, we include here the fundamental series of iron lines from helium-like and hydrogen-like ions, and fluorescent Kα and Kβ lines from low ionized iron. We consider two cases: nonrotating black hole, and black hole rotating with almost maximum spin a = 0.98, and obtain spectra for five accretion disks from hard X-rays to the infrared. Results: In nonirradiated disks, resonance lines from He-like and H-like iron appear mostly in absorption. Such disk spectra exhibit limb darkening in the whole energy range. External irradiation causes that iron resonance lines appear in emission. Furthermore, depending on disk effective temperature, fluorescent iron Kα and Kβ lines are present in disk emitting spectra. All models with irradiation exhibit limb brightening in their X-ray reflected continua. Conclusions: We show that the disk around stellar black hole itself is hot enough to produce strong-absorption resonance lines of iron. Emission lines can only be observed if heating by external X-rays dominates thermal processess in a hot disk atmosphere. Irradiated disks are usually brighter in X-ray continuum when seen edge on, and fainter when seen face on.

  6. Direct on-strip analysis of size- and time-resolved aerosol impactor samples using laser induced fluorescence spectra excited at 263 and 351 nm.

    PubMed

    Wang, Chuji; Pan, Yong-Le; James, Deryck; Wetmore, Alan E; Redding, Brandon

    2014-04-11

    We report a novel atmospheric aerosol characterization technique, in which dual wavelength UV laser induced fluorescence (LIF) spectrometry marries an eight-stage rotating drum impactor (RDI), namely UV-LIF-RDI, to achieve size- and time-resolved analysis of aerosol particles on-strip. The UV-LIF-RDI technique measured LIF spectra via direct laser beam illumination onto the particles that were impacted on a RDI strip with a spatial resolution of 1.2mm, equivalent to an averaged time resolution in the aerosol sampling of 3.6 h. Excited by a 263 nm or 351 nm laser, more than 2000 LIF spectra within a 3-week aerosol collection time period were obtained from the eight individual RDI strips that collected particles in eight different sizes ranging from 0.09 to 10 μm in Djibouti. Based on the known fluorescence database from atmospheric aerosols in the US, the LIF spectra obtained from the Djibouti aerosol samples were found to be dominated by fluorescence clusters 2, 5, and 8 (peaked at 330, 370, and 475 nm) when excited at 263 nm and by fluorescence clusters 1, 2, 5, and 6 (peaked at 390 and 460 nm) when excited at 351 nm. Size- and time-dependent variations of the fluorescence spectra revealed some size and time evolution behavior of organic and biological aerosols from the atmosphere in Djibouti. Moreover, this analytical technique could locate the possible sources and chemical compositions contributing to these fluorescence clusters. Advantages, limitations, and future developments of this new aerosol analysis technique are also discussed. Published by Elsevier B.V.

  7. 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.

  8. 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.

  9. Laser Induced Fluorescence Spectroscopy of Neutral and Ionized Polycyclic Aromatic Hydrocarbons in a Cosmic Simulation Chamber

    NASA Astrophysics Data System (ADS)

    Bejaoui, Salma; Salama, Farid

    2015-08-01

    Polycyclic aromatic hydrocarbon (PAH) molecules are considered the best carriers to account for the ubiquitous infrared emission bands. PAHs have also been proposed as candidates to explain the diffuse interstellar bands (DIBs), a series of absorption features seen on the interstellar extinction curve and are plausible carriers for the extended red emission (ERE), a photoluminescent process associated with a wide variety of interstellar environments. Extensive efforts have been devoted over the past two decades to characterize the physical and chemical properties of PAH molecules and ions in space. Absorption spectra of PAH molecules and ions trapped in solid matrices have been compared to the DIBs [1, 2]. Absorption spectra of several cold, isolated gas-phase PAHs have also been measured under experimental conditions that mimic the interstellar conditions [see 3 for a review]. The purpose of this study is to provide a new dimension to the existing spectroscopic database of neutral and single ionized PAHs that is largely based on absorption spectra by adding emission spectroscopy data. The measurements are based on the laser-induced fluorescence (LIF) technique [4] and are performed with the Pulsed Discharge Nozzle (PDN) of the COSmIC laboratory facility at NASA Ames laboratory. The PDN generates plasma in a free supersonic jet expansion to simulate the physical and the chemical conditions in interstellar environments. We focus, here, on the fluorescence spectra of large neutral PAHs and their cations where there is a lack of fluorescence spectroscopy data. The astronomical implications of the data (e.g., ERE) are examinedReferences[1] F. Salama, E. Bakes, L.J. Allamandola, A.G.G.M. Tielens, Astrophys. J., 458 (1996) p.621[2] F. Salama, The ISO Revolution, EDP Sciences, Les Ulis, France (1999) p.65[3] Salama F., In Organic Matter in Space, IAU Symposium 251, Kwok & Sandford Eds.Cambridge University Press,4, S251,(2008), p. 357 (2008) and references therein.[4

  10. Application of support vector machine method for the analysis of absorption spectra of exhaled air of patients with broncho-pulmonary diseases

    NASA Astrophysics Data System (ADS)

    Bukreeva, Ekaterina B.; Bulanova, Anna A.; Kistenev, Yury V.; Kuzmin, Dmitry A.; Tuzikov, Sergei A.; Yumov, Evgeny L.

    2014-11-01

    The results of the joint use of laser photoacoustic spectroscopy and chemometrics methods in gas analysis of exhaled air of patients with respiratory diseases (chronic obstructive pulmonary disease, pneumonia and lung cancer) are presented. The absorption spectra of exhaled breath of all volunteers were measured, the classification methods of the scans of the absorption spectra were applied, the sensitivity/specificity of the classification results were determined. It were obtained a result of nosological in pairs classification for all investigated volunteers, indices of sensitivity and specificity.

  11. Electronic and nuclear contributions to time-resolved optical and X-ray absorption spectra of hematite and insights into photoelectrochemical performance

    DOE PAGES

    Hayes, Dugan; Hadt, Ryan G.; Emery, Jonathan D.; ...

    2016-11-02

    Ultrafast time-resolved studies of photocatalytic thin films can provide a wealth of information crucial for understanding and thereby improving the performance of these materials by directly probing electronic structure, reaction intermediates, and charge carrier dynamics. The interpretation of transient spectra, however, can be complicated by thermally induced structural distortions, which appear within the first few picoseconds following excitation due to carrier–phonon scattering. Here we present a comparison of ex situ steady-state thermal difference spectra and transient absorption spectra spanning from NIR to hard X-ray energies of hematite thin films grown by atomic layer deposition. We find that beyond the firstmore » 100 picoseconds, the transient spectra measured for all excitation wavelengths and probe energies are almost entirely due to thermal effects as the lattice expands in response to the ultrafast temperature jump and then cools to room temperature on the microsecond timescale. At earlier times, a broad excited state absorption band that is assigned to free carriers appears at 675 nm, and the lifetime and shape of this feature also appear to be mostly independent of excitation wavelength. The combined spectroscopic data, which are modeled with density functional theory and full multiple scattering calculations, support an assignment of the optical absorption spectrum of hematite that involves two LMCT bands that nearly span the visible spectrum. Lastly, our results also suggest a framework for shifting the ligand-to-metal charge transfer absorption bands of ferric oxide films from the near-UV further into the visible part of the solar spectrum to improve solar conversion efficiency.« less

  12. Self-interaction-corrected time-dependent density-functional-theory calculations of x-ray-absorption spectra

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Tu, Guangde; Rinkevicius, Zilvinas; Vahtras, Olav

    We outline an approach within time-dependent density functional theory that predicts x-ray spectra on an absolute scale. The approach rests on a recent formulation of the resonant-convergent first-order polarization propagator [P. Norman et al., J. Chem. Phys. 123, 194103 (2005)] and corrects for the self-interaction energy of the core orbital. This polarization propagator approach makes it possible to directly calculate the x-ray absorption cross section at a particular frequency without explicitly addressing the excited-state spectrum. The self-interaction correction for the employed density functional accounts for an energy shift of the spectrum, and fully correlated absolute-scale x-ray spectra are thereby obtainedmore » based solely on optimization of the electronic ground state. The procedure is benchmarked against experimental spectra of a set of small organic molecules at the carbon, nitrogen, and oxygen K edges.« less

  13. A Statistical Study of the Southern Fermi Bubble in UV Absorption Spectra

    NASA Astrophysics Data System (ADS)

    Karim, Md. Tanveer; Fox, Andrew; Jenkins, Edward; Bordoloi, Rongmon; Wakker, Bart; Savage, Blair D.; Lockman, Felix; Crawford, Steve; Bland-Hawthorn, Joss; Jorgenson, Regina A.

    2018-01-01

    The Fermi Bubbles are two giant lobes of plasma situated at the center of the Milky Way, extending 55° above and below the Galactic Midplane. Although the Bubbles have been widely studied in multiple wavelengths, few studies have been done in UV absorption. Here we present a statistical study of the Southern Fermi Bubble using 17 QSO sightlines — 6 inside the Bubble, 11 outside — using UV absorption spectra from the Hubble Space Telescope Cosmic Origins Spectrograph (HST/COS). We searched for high-velocity clouds (HVCs) in 11 metal lines from ions of Aluminium, Carbon and Silicon. We detected HVCs in 83% of the sightlines inside the Bubble and 64% outside the Bubble, showing an enhancement in the covering fraction of HVCs in the Southern Bubble region. We also observed a decrease in vLSR of the HVCs as a function of the galactic latitude, consistent with a scenario where the identified HVCs trace the Galactic nuclear outflow, as sightlines closer to the central engine are expected to show a higher velocity. Combined with previous studies, our analysis indicates that the Southern Fermi Bubble is a dynamic environment giving rise to complex absorption features.

  14. A new selective fluorescent sensor for Fe3+ based on a pyrazoline derivative.

    PubMed

    Hu, Shengli; Zhang, Shushu; Gao, Chan; Xu, Caihua; Gao, Qing

    2013-09-01

    A new pyrazoline derivative was designed and synthesized. The structure of the pyrazoline was confirmed by single crystal X-ray diffraction and its photophysical properties were studied by absorption and fluorescence spectra. This compound can be used to determine Fe(3+) ion with high selectivity among a series of cations in tetrahydrofuran and even in aqueous tetrahydrofuran. This sensor forms a 1:1 complex with Fe(3+) and displays fluorescent quenching. Copyright © 2013 Elsevier B.V. All rights reserved.

  15. 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…

  16. Measurements of spectral parameters of water-vapour transitions near 1388 and 1345 nm for accurate simulation of high-pressure absorption spectra

    NASA Astrophysics Data System (ADS)

    Liu, Xiang; Jeffries, Jay B.; Hanson, Ronald K.

    2007-05-01

    Quantitative near-infrared absorption spectroscopy of water-vapour overtone and combination bands at high pressures is complicated by pressure broadening and shifting of individual lines and the blending of neighbouring transitions. An experimental and computational methodology is developed to determine accurate high-pressure absorption spectra. This case study investigates two water-vapour transitions, one near 1388 nm (7203.9 cm-1) and the other near 1345 nm (7435.6 cm-1), for potential two-line absorption measurements of temperature in the range of 400-1050 K with a pressure varying from 5-25 atm. The required quantitative spectroscopy data (line strength, collisional broadening, and pressure-induced frequency shift) of the target transitions and their neighbours (a total of four H2O vapour transitions near 1388 nm and six transitions near 1345 nm) are measured in neat H2O vapour, H2O-air and H2O-CO2 mixtures as a function of temperature (296-1000 K) at low pressures (<800 Torr). Precise values of the line strength S(T), pressure-broadening coefficients γair(T) and \\gamma _{CO_2 } (T), and pressure-shift coefficients δair(T) and \\delta _{CO_2 } (T) for the ten transitions were inferred from the measured spectra and compared with data from HITRAN 2004. A hybrid spectroscopic database was constructed by modifying HITRAN 2004 to incorporate these values for simulation of water-vapour-absorption spectra at high pressures. Simulations using this hybrid database are in good agreement with high pressure experiments and demonstrate that data collected at modest pressures can be used to simulate high-pressure absorption spectra.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed Central

    Guo, Zijian; Favazza, Christopher; Garcia-Uribe, Alejandro

    2012-01-01

    Abstract. 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. PMID:22734767

  19. 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.

  20. Classification of different kinds of pesticide residues on lettuce based on fluorescence spectra and WT-BCC-SVM algorithm

    NASA Astrophysics Data System (ADS)

    Zhou, Xin; Jun, Sun; Zhang, Bing; Jun, Wu

    2017-07-01

    In order to improve the reliability of the spectrum feature extracted by wavelet transform, a method combining wavelet transform (WT) with bacterial colony chemotaxis algorithm and support vector machine (BCC-SVM) algorithm (WT-BCC-SVM) was proposed in this paper. Besides, we aimed to identify different kinds of pesticide residues on lettuce leaves in a novel and rapid non-destructive way by using fluorescence spectra technology. The fluorescence spectral data of 150 lettuce leaf samples of five different kinds of pesticide residues on the surface of lettuce were obtained using Cary Eclipse fluorescence spectrometer. Standard normalized variable detrending (SNV detrending), Savitzky-Golay coupled with Standard normalized variable detrending (SG-SNV detrending) were used to preprocess the raw spectra, respectively. Bacterial colony chemotaxis combined with support vector machine (BCC-SVM) and support vector machine (SVM) classification models were established based on full spectra (FS) and wavelet transform characteristics (WTC), respectively. Moreover, WTC were selected by WT. The results showed that the accuracy of training set, calibration set and the prediction set of the best optimal classification model (SG-SNV detrending-WT-BCC-SVM) were 100%, 98% and 93.33%, respectively. In addition, the results indicated that it was feasible to use WT-BCC-SVM to establish diagnostic model of different kinds of pesticide residues on lettuce leaves.

  1. Ne matrix spectra of the sym-C6Br3F3+ radical cation

    USGS Publications Warehouse

    Bondybey, V.E.; Sears, T.J.; Miller, T.A.; Vaughn, C.; English, J.H.; Shiley, R.S.

    1981-01-01

    The electronic absorption and laser excited, wavelength resolved fluorescence spectra of the title cation have been observed in solid Ne matrix and vibrationally analysed. The vibrational structure of the excited B2A2??? state shows close similarity to the parent compound. The X2E??? ground state structure is strongly perturbed and irregular owing to a large Jahn-Teller distortion. The data are analysed in terms of a recently developed, sophisticated multimode Jahn-Teller theoretical model. We have generated the sym-C6Br3F3+ cations in solid Ne matrix and obtained their wavelength resolved emission and absorption spectra. T ground electronic X2E??? state exhibits an irregular and strongly perturbed vibrational structure, which can be successfully modeled using sophisticated multimode Jahn-Teller theory. ?? 1981.

  2. VizieR Online Data Catalog: Sgr B2 los molecular absorption line spectra (Corby+, 2018)

    NASA Astrophysics Data System (ADS)

    Corby, J. F.; McGuire, B. A.; Herbst, E.; Remijan, A. J.

    2017-11-01

    Spectra covering transitions of c-C3H2, c-H1 SO, CCS, H2CS, HCS+, OH, SiO, 29SiO, H2CO, H2(13C)O, l-C3H, and l-C3H+ with line-of-sight absorption observed in the 1-50 GHz data from the PRebiotic Interstellar MOlecular Survey (PRIMOS) taken with the Robert C. Byrd Green Bank Telescope (GBT). Data were observed between 2001 and 2014, with the majority of the data obtained in 2007 in GBT Key Science project ID GBT07A-051. Spectra have been baseline-subtracted using best fit polynomials as described in the paper, and normalized by the continuum, so that the y-axis represents (T/TC-1). Data are provided in the FITS format; each FITS file contains all lines of a single molecule that are observed to have foreground absorption. Please refer to Table 1 of the paper to obtain molecular transition rest frequencies, energies, GBT beam sizes, and transition quantum numbers. (2 data files).

  3. Two-photon fluorescence and fluorescence imaging of two styryl heterocyclic dyes combined with DNA

    NASA Astrophysics Data System (ADS)

    Gao, Chao; Liu, Shu-yao; Zhang, Xian; Liu, Ying-kai; Qiao, Cong-de; Liu, Zhao-e.

    2016-03-01

    Two new styryl heterocyclic two-photon (TP) materials, 4-[4-(N-methyl)styrene]-imidazo [4,5-f][1,10] phenanthroline-benzene iodated salt (probe-1) and 4,4- [4-(N-methyl)styrene] -benzene iodated salt (probe-2) were successfully synthesized and studied as potential fluorescent probes of DNA detection. The linear and nonlinear photophysical properties of two compounds in different solvents were investigated. The absorption, one- and two-photon fluorescent spectra of the free dye and dye-DNA complex were also examined to evaluate their photophysical properties. The binding constants of dye-DNA were obtained according to Scatchard equation with good values. The results showed that two probes could be used as fluorescent DNA probes by two-photon excitation, and TP fluorescent properties of probe-1 are superior to that of probe-2. The fluorescent method date indicated that the mechanisms of dye-DNA complex interaction may be groove binding for probe-1 and electrostatic interaction for probe-2, respectively. The MTT assay experiments showed two probes are low toxicity. Moreover, the TP fluorescence imaging of DNA detection in living cells at 800 nm indicated that the ability to locate in cell nuclei of probe-1 is better than that of probe-2.

  4. Two-photon fluorescence and fluorescence imaging of two styryl heterocyclic dyes combined with DNA.

    PubMed

    Gao, Chao; Liu, Shu-yao; Zhang, Xian; Liu, Ying-kai; Qiao, Cong-de; Liu, Zhao-e

    2016-03-05

    Two new styryl heterocyclic two-photon (TP) materials, 4-[4-(N-methyl)styrene]-imidazo [4,5-f][1,10] phenanthroline-benzene iodated salt (probe-1) and 4,4-[4-(N-methyl)styrene]-benzene iodated salt (probe-2) were successfully synthesized and studied as potential fluorescent probes of DNA detection. The linear and nonlinear photophysical properties of two compounds in different solvents were investigated. The absorption, one- and two-photon fluorescent spectra of the free dye and dye-DNA complex were also examined to evaluate their photophysical properties. The binding constants of dye-DNA were obtained according to Scatchard equation with good values. The results showed that two probes could be used as fluorescent DNA probes by two-photon excitation, and TP fluorescent properties of probe-1 are superior to that of probe-2. The fluorescent method date indicated that the mechanisms of dye-DNA complex interaction may be groove binding for probe-1 and electrostatic interaction for probe-2, respectively. The MTT assay experiments showed two probes are low toxicity. Moreover, the TP fluorescence imaging of DNA detection in living cells at 800 nm indicated that the ability to locate in cell nuclei of probe-1 is better than that of probe-2. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. Thermally activated delayed fluorescence of fluorescein derivative for time-resolved and confocal fluorescence imaging.

    PubMed

    Xiong, Xiaoqing; Song, Fengling; Wang, Jingyun; Zhang, Yukang; Xue, Yingying; Sun, Liangliang; Jiang, Na; Gao, Pan; Tian, Lu; Peng, Xiaojun

    2014-07-09

    Compared with fluorescence imaging utilizing fluorophores whose lifetimes are in the order of nanoseconds, time-resolved fluorescence microscopy has more advantages in monitoring target fluorescence. In this work, compound DCF-MPYM, which is based on a fluorescein derivative, showed long-lived luminescence (22.11 μs in deaerated ethanol) and was used in time-resolved fluorescence imaging in living cells. Both nanosecond time-resolved transient difference absorption spectra and time-correlated single-photon counting (TCSPC) were employed to explain the long lifetime of the compound, which is rare in pure organic fluorophores without rare earth metals and heavy atoms. A mechanism of thermally activated delayed fluorescence (TADF) that considers the long wavelength fluorescence, large Stokes shift, and long-lived triplet state of DCF-MPYM was proposed. The energy gap (ΔEST) of DCF-MPYM between the singlet and triplet state was determined to be 28.36 meV by the decay rate of DF as a function of temperature. The ΔE(ST) was small enough to allow efficient intersystem crossing (ISC) and reverse ISC, leading to efficient TADF at room temperature. The straightforward synthesis of DCF-MPYM and wide availability of its starting materials contribute to the excellent potential of the compound to replace luminescent lanthanide complexes in future time-resolved imaging technologies.

  6. Diiodobodipy-styrylbodipy Dyads: Preparation and Study of the Intersystem Crossing and Fluorescence Resonance Energy Transfer.

    PubMed

    Wang, Zhijia; Xie, Yun; Xu, Kejing; Zhao, Jianzhang; Glusac, Ksenija D

    2015-07-02

    2,6-Diiodobodipy-styrylbodipy dyads were prepared to study the competing intersystem crossing (ISC) and the fluorescence-resonance-energy-transfer (FRET), and its effect on the photophysical property of the dyads. In the dyads, 2,6-diiodobodipy moiety was used as singlet energy donor and the spin converter for triplet state formation, whereas the styrylbodipy was used as singlet and triplet energy acceptors, thus the competition between the ISC and FRET processes is established. The photophysical properties were studied with steady-state UV-vis absorption and fluorescence spectroscopy, electrochemical characterization, and femto/nanosecond time-resolved transient absorption spectroscopies. FRET was confirmed with steady state fluorescence quenching and fluorescence excitation spectra and ultrafast transient absorption spectroscopy (kFRET = 5.0 × 10(10) s(-1)). The singlet oxygen quantum yield (ΦΔ = 0.19) of the dyad was reduced as compared with that of the reference spin converter (2,6-diiodobodipy, ΦΔ = 0.85), thus the ISC was substantially inhibited by FRET. Photoinduced intramolecular electron transfer (ET) was studied by electrochemical data and fluorescence quenching. Intermolecular triplet energy transfer was studied with nanosecond transient absorption spectroscopy as an efficient (ΦTTET = 92%) and fast process (kTTET = 5.2 × 10(4) s(-1)). These results are useful for designing organic triplet photosensitizers and for the study of the photophysical properties.

  7. Long-Range Chemical Sensitivity in the Sulfur K-Edge X-ray Absorption Spectra of Substituted Thiophenes

    PubMed Central

    2015-01-01

    Thiophenes are the simplest aromatic sulfur-containing compounds and are stable and widespread in fossil fuels. Regulation of sulfur levels in fuels and emissions has become and continues to be ever more stringent as part of governments’ efforts to address negative environmental impacts of sulfur dioxide. In turn, more effective removal methods are continually being sought. In a chemical sense, thiophenes are somewhat obdurate and hence their removal from fossil fuels poses problems for the industrial chemist. Sulfur K-edge X-ray absorption spectroscopy provides key information on thiophenic components in fuels. Here we present a systematic study of the spectroscopic sensitivity to chemical modifications of the thiophene system. We conclude that while the utility of sulfur K-edge X-ray absorption spectra in understanding the chemical composition of sulfur-containing fossil fuels has already been demonstrated, care must be exercised in interpreting these spectra because the assumption of an invariant spectrum for thiophenic forms may not always be valid. PMID:25116792

  8. Alteration of fluorescent protein spectroscopic properties upon cryoprotection.

    PubMed

    von Stetten, David; Batot, Gaëlle O; Noirclerc-Savoye, Marjolaine; Royant, Antoine

    2012-11-01

    Cryoprotection of a protein crystal by addition of small-molecule compounds may sometimes affect the structure of its active site. The spectroscopic and structural effects of the two cryoprotectants glycerol and ethylene glycol on the cyan fluorescent protein Cerulean were investigated. While glycerol had almost no noticeable effect, ethylene glycol was shown to induce a systematic red shift of the UV-vis absorption and fluorescence emission spectra. Additionally, ethylene glycol molecules were shown to enter the core of the protein, with one of them binding in close vicinity to the chromophore, which provides a sound explanation for the observed spectroscopic changes. These results highlight the need to systematically record spectroscopic data on crystals of light-absorbing proteins and reinforce the notion that fluorescent proteins must not been seen as rigid structures.

  9. The origin of absorptive features in the two-dimensional electronic spectra of rhodopsin.

    PubMed

    Farag, Marwa H; Jansen, Thomas L C; Knoester, Jasper

    2018-05-09

    In rhodopsin, the absorption of a photon causes the isomerization of the 11-cis isomer of the retinal chromophore to its all-trans isomer. This isomerization is known to occur through a conical intersection (CI) and the internal conversion through the CI is known to be vibrationally coherent. Recently measured two-dimensional electronic spectra (2DES) showed dramatic absorptive spectral features at early waiting times associated with the transition through the CI. The common two-state two-mode model Hamiltonian was unable to elucidate the origin of these features. To rationalize the source of these features, we employ a three-state three-mode model Hamiltonian where the hydrogen out-of plane (HOOP) mode and a higher-lying electronic state are included. The 2DES of the retinal chromophore in rhodopsin are calculated and compared with the experiment. Our analysis shows that the source of the observed features in the measured 2DES is the excited state absorption to a higher-lying electronic state and not the HOOP mode.

  10. Foliar Reflectance and Fluorescence Responses for Corn and Soybean Plants Under Nitrogen Stress

    NASA Technical Reports Server (NTRS)

    Middleton, E. M.; Campbell, P. K. Entcheva; Corp, L. A.; Butcher, L. M.; McMurtrey, J. E.

    2003-01-01

    We are investigating the use of spectral indices derived from actively induced fluorescence spectra and passive optical spectra. We examined the influence of photosynthetic pigment, carbon (C) and nitrogen (N) content on the spectral fluorescence and passive optical property characteristics of mature, upper leaves from plants provided different N fertilizer application rates: 20%, 50%, 100% and 150% of recommended N levels. A suite of optical, fluorescence, and biophysical measurements were collected on leaves from field grown corn (Zea mays L.) and soybean plants (Glycine max L.) grown in pots (greenhouse + ambient sunlight. Steady state laser-induced fluorescence emission spectra (5 nm resolution) were obtained from adaxial and abaxial surfaces resulting from excitation at single wavelengths (280, 380 or 360, and 532 nm). For emission spectra produced by each of these excitation wavelengths, ratios of emission peaks were calculated, including the red far-red chlorophyll fluorescence (ChlF) ratio (F685/F740) and the far-red/green (F740/F525) ratio. High resolution (< 3 nm) optical spectra (350-2500 nm) of reflectance, transmittance, and absorptance were also acquired for both adaxial and abaxial leaf surfaces. Species differences were demonstrated for several optical parameters. A 'red edge' derivative ratio determined from transmittance spectra [as the maximum first deivative, between 650-750 nm, normalized to the value at 744 nm, or Dmax/D744], was strongly associated with the C/N ratio (r(exp 2) = 0.90, P +/- 0.001). This ratio, calculated from reflectance spectra, was inversely related to chlorophyll b content (r(exp 2) = 0.91, P +/- 0.001) as was the ChlF (F685/F740) ratio obtained with 532 nm excitation (r(exp 2) = 0.76, P +/- 0.01). Discrimination of N treatment groups was possible with specific fluorescence band ratios (e.g., F740/F525 obtained with 380 nm excitation). Higher ChlF and blue-green emissions were measured from the abaxial leaf surfaces

  11. Visible absorption properties of radiation exposed XR type-T radiochromic film.

    PubMed

    Butson, Martin J; Cheung, Tsang; Yu, Peter K N

    2004-10-07

    The visible absorption spectra of Gafchromic XR type-T radiochromic film have been investigated to analyse the dosimetry characteristics of the film with visible light densitometers. Common densitometers can use photospectrometry, fluorescent light (broad-band visible), helium neon (632 nm), light emitting diode (LED) or other specific bandwidth spectra. The visible absorption spectra of this film when exposed to photon radiation show peaks at 676 nm and 618 nm at 2 Gy absorbed doses which shift to slightly lower wavelengths (662 nm and 612 nm at 8 Gy absorbed dose) at higher doses. This is similar to previous models of Gafchromic film such as MD-55-2 and HS but XR type-T also includes a large absorption at lower visible wavelengths due to 'yellow' dyes placed within the film to aid with visible recognition of the film exposure level. The yellow dye band pass is produced at approximately 520 nm to 550 nm and absorbs wavelengths lower than this value within the visible spectrum. This accounts for the colour change from yellow to brown through the added absorption in the red wavelengths with radiation exposure. The film produces a relatively high dose sensitivity with up to 0.25 OD units per Gy change at 672 nm at 100 kVp x-ray energy. Variations in dose sensitivity can be achieved by varying wavelength analysis.

  12. Substituent and solvent effects on the UV/vis absorption spectra of 5-(3- and 4-substituted arylazo)-4,6-dimethyl-3-cyano-2-pyridones

    NASA Astrophysics Data System (ADS)

    Mijin, Dušan Ž.; Ušćumlić, Gordana S.; Perišić-Janjić, Nada U.; Valentić, Nataša V.

    2006-01-01

    Absorption spectra of seventeen 5-(3- and 4-substituted arylazo)-4,6-dimethyl-3-cyano-2-pyridones have been recorded in 12 protic and aprotic solvents in the range 200-600 nm. The effects of substituents on the absorption spectra of these new azo dyes are interpreted by correlation of absorption frequencies with Hammett equation. The solute-solvent interactions were clarified on the basis of linear solvation energy relationships concept proposed by Kamlet and Taft. The 2-pyridone/2-hydroxypiridine tautomeric equilibration is found to depend upon substituents as well as on solvents.

  13. Laser-Induced Fluorescence Measurements for Optical Single Atom Detection for Nuclear Astrophysics

    NASA Astrophysics Data System (ADS)

    Parzuchowski, Kristen; Singh, Jaideep; Wenzl, Jennifer; Frisbie, Dustin; Johnson, Maegan

    2016-09-01

    We propose a new highly selective detector to measure rare nuclear reactions relevant for nuclear astrophysics. Our primary interest is the 22Ne(α , n) 25Mg reaction, which is a primary source of neutrons for the s-process. Our proposed detector, in conjunction with a recoil separator, captures the recoil products resulting from the reaction in a cryogenically frozen thin film of solid neon. The fluorescence spectra of the captured atoms is shifted from the absorption spectra by hundreds of nanometers. This allows for the optical detection of individual fluorescence photons against a background of intense excitation light. We will describe our initial studies of laser-induced fluorescence of Yb and Mg in solid Ne. Neon is an attractive medium because it is optically transparent and provides efficient, pure, stable, & chemically inert confinement for a wide variety of atomic and molecular species. Yb is used as a test atom because of its similar atomic structure to Mg and much brighter fluorescence signal. This work is supported by funds from Michigan State University.

  14. The IR Absorption Spectra of Aqueous Solutions of Dimethylsulfoxide over the Frequency Range 50-300 cm-1 and the Mobility of Water Molecules

    NASA Astrophysics Data System (ADS)

    Klemenkova, Z. S.; Novskova, T. A.; Lyashchenko, A. K.

    2008-04-01

    The IR absorption spectra of aqueous solutions of dimethylsulfoxide (DMSO) with concentrations from 100% H2O to 100% DMSO were recorded over the frequency range 50-500 cm-1. The absorption spectra were described using the theoretical scheme of hindered rotators. A model was developed according to which orientation relaxation in solution was related to separate rotations of H2O and DMSO molecules through fixed small and (or) large angles in a unified network of H-bonds consisting of several subsystems ordered to various degrees. The calculated absorption spectra were in agreement with the experimental data in the far IR region. Elementary motions of molecules were found to slow down in the passage from pure dimethylsulfoxide to its aqueous solutions. The special features of the hydrophilic and hydrophobic hydration of DMSO polar and nonpolar groups were considered.

  15. Effects of phonon broadening on x-ray near-edge spectra in molecular crystals

    NASA Astrophysics Data System (ADS)

    Vinson, John; Jach, Terrence; Elam, Tim; Denlinger, Jonathon

    2014-03-01

    Calculations of near-edge x-ray spectra are often carried out using the average atomic coordinates from x-ray or neutron scattering experiments or from density functional theory (DFT) energy minimization. This neglects disorder from thermal and zero-point vibrations. Here we look at the nitrogen K-edge of ammonium chloride and ammonium nitrate, comparing Bethe-Salpeter calculations of absorption and fluorescence to experiment. We find that intra-molecular vibrational effects lead to significant, non-uniform broadening of the spectra, and that for some features zero-point motion is the primary source of the observed shape.

  16. Carbon X-ray absorption in the local ISM: fingerprints in X-ray Novae spectra

    NASA Astrophysics Data System (ADS)

    Gatuzz, Efraín; Ness, J.-U.; Gorczyca, T. W.; Hasoglu, M. F.; Kallman, Timothy R.; García, Javier A.

    2018-06-01

    We present a study of the C K-edge using high-resolution LETGS Chandra spectra of four novae during their super-soft-source (SSS) phase. We identified absorption lines due to C II Kα, C III Kα and C III Kβ resonances. We used these astronomical observations to perform a benchmarking of the atomic data, which involves wavelength shifts of the resonances and photoionization cross-sections. We used improved atomic data to estimate the C II and C III column densities. The absence of physical shifts for the absorption lines, the consistence of the column densities between multiple observations and the high temperature required for the SSS nova atmosphere modeling support our conclusion about an ISM origin of the respective absorption lines. Assuming a collisional ionization equilibrium plasma the maximum temperature derived from the ratio of C II/C III column densities of the absorbers correspond to Tmax < 3.05 × 104 K.

  17. Temperature dependent fluorescence spectra arise from change in excited-state intramolecular proton transfer potential of 4‧-N,N-dimethylamino-3-hydroxyflavone-doped acetonitrile crystals

    NASA Astrophysics Data System (ADS)

    Furukawa, Kazuki; Yamamoto, Norifumi; Hino, Kazuyuki; Sekiya, Hiroshi

    2016-01-01

    The effect of intermolecular interaction on excited-state intramolecular proton transfer (ESIPT) in 4‧-N,N-dimethylamino-3-hydroxyflavone (DMHF) doped in acetonitrile crystals was investigated by measuring the temperature dependence of fluorescence excitation and fluorescence spectra. A solid/solid phase transition of DMHF-doped acetonitrile crystals occurred in the temperature between 210 and 218 K. Significant differences in the spectral profiles and shifts in the fluorescence spectra were observed in the low- and high-temperature regions of the phase transition. The temperature dependence of the ESIPT potential of DMHF is discussed.

  18. Investigation of the multiplet features of SrTiO 3 in X-ray absorption spectra based on configuration interaction calculations

    DOE PAGES

    Wu, M.; Xin, Houlin L.; Wang, J. O.; ...

    2018-04-24

    Synchrotron-based L 2,3-edge absorption spectra show strong sensitivities to the local electronic structure and chemical environment. However, detailed physical information cannot be extracted easily without computational aids. Here in this study using the experimental Ti L 2,3-edges absorption spectrum of SrTiO 3as a fingerprint and considering full multiplet effects, calculations yield different energy parameters characterizing local ground state properties. The peak splitting and intensity ratios of the L 3 and L 2 set of peaks are carefully analyzed quantitatively, giving rise to a small hybridization energy around 1.2 eV, and the different hybridization energy values reported in the literature aremore » further addressed. Finally, absorption spectra with different linearly polarized photons under various tetragonal crystal fields are investigated, revealing a non-linear orbital–lattice interaction, and a theoretical guidance for material engineering of SrTiO 3-based thin films and heterostructures is offered. Finally, detailed analysis of spectrum shifts with different tetragonal crystal fields suggests that the e g crystal field splitting is a necessary parameter for a thorough analysis of the spectra, even though it is not relevant for the ground state properties.« less

  19. Investigation of the multiplet features of SrTiO 3 in X-ray absorption spectra based on configuration interaction calculations

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Wu, M.; Xin, Houlin L.; Wang, J. O.

    Synchrotron-based L 2,3-edge absorption spectra show strong sensitivities to the local electronic structure and chemical environment. However, detailed physical information cannot be extracted easily without computational aids. Here in this study using the experimental Ti L 2,3-edges absorption spectrum of SrTiO 3as a fingerprint and considering full multiplet effects, calculations yield different energy parameters characterizing local ground state properties. The peak splitting and intensity ratios of the L 3 and L 2 set of peaks are carefully analyzed quantitatively, giving rise to a small hybridization energy around 1.2 eV, and the different hybridization energy values reported in the literature aremore » further addressed. Finally, absorption spectra with different linearly polarized photons under various tetragonal crystal fields are investigated, revealing a non-linear orbital–lattice interaction, and a theoretical guidance for material engineering of SrTiO 3-based thin films and heterostructures is offered. Finally, detailed analysis of spectrum shifts with different tetragonal crystal fields suggests that the e g crystal field splitting is a necessary parameter for a thorough analysis of the spectra, even though it is not relevant for the ground state properties.« less

  20. FRET-based small-molecule fluorescent probes: rational design and bioimaging applications.

    PubMed

    Yuan, Lin; Lin, Weiying; Zheng, Kaibo; Zhu, Sasa

    2013-07-16

    Fluorescence imaging has emerged as a powerful tool for monitoring biomolecules within the context of living systems with high spatial and temporal resolution. Researchers have constructed a large number of synthetic intensity-based fluorescent probes for bio-imaging. However, intensity-based fluorescent probes have some limitations: variations in probe concentration, probe environment, and excitation intensity may influence the fluorescence intensity measurements. In principle, the use of ratiometric fluorescent probes can alleviate this shortcoming. Förster resonance energy transfer (FRET) is one of the most widely used sensing mechanisms for ratiometric fluorescent probes. However, the development of synthetic FRET probes with favorable photophysical properties that are also suitable for biological imaging applications remains challenging. In this Account, we review the rational design and biological applications of synthetic FRET probes, focusing primarily on studies from our laboratory. To construct useful FRET probes, it is a pre-requisite to develop a FRET platform with favorable photophysical properties. The design criteria of a FRET platform include (1) well-resolved absorption spectra of the donor and acceptor, (2) well-separated emission spectra of the donor and acceptor, (3) donors and acceptors with comparable brightness, (4) rigid linkers, and (5) near-perfect efficiency in energy transfer. With an efficient FRET platform in hand, it is then necessary to modulate the donor-acceptor distance or spectral overlap integral in an analyte-dependent fashion for development of FRET probes. Herein, we emphasize our most recent progress on the development of FRET probes by spectral overlap integral, in particular by changing the molar absorption coefficient of the donor dyes such as rhodamine dyes, which undergo unique changes in the absorption profiles during the ring-opening and -closing processes. Although partial success has been obtained in design of

  1. Influence of polarity of solvents on IR absorption and Raman spectra of ascorbic acid

    NASA Astrophysics Data System (ADS)

    Kutsenko, S. A.; Danyaeva, Y. S.; Maximova, S. V.

    2018-04-01

    The results of numerical calculations of IR absorption and Raman spectra of ascorbic acid in polar and nonpolar solutions are presented. The dependence of the change in the total energy and the dipole moment of the molecule on the characteristics of the solvents was investigated using the two solvation models. Spectral bands and the corresponding structural groups of the molecule are found, the characteristics of which are most vulnerable to solvents.

  2. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2006-09-01

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

  4. Resonant Raman scattering background in XRF spectra of binary samples

    NASA Astrophysics Data System (ADS)

    Sánchez, Héctor Jorge; Leani, Juan José

    2015-02-01

    In x-ray fluorescence analysis, spectra present singular characteristics produced by the different scattering processes. When atoms are irradiated with incident energy lower and close to an absorption edge, scattering peaks appear due to an inelastic process known as resonant Raman scattering. In this work we present theoretical calculations of the resonant Raman scattering contributions to the background of x-ray fluorescence spectra of binary samples of current technological or biological interest. On one hand, a binary alloy of Fe with traces of Mn (Mn: 0.01%, Fe: 99.99%) was studied because of its importance in the stainless steels industries. On the second hand a pure sample of Ti with V traces (Ti: 99%, V: 1%) was analyzed due to the current relevance in medical applications. In order to perform the calculations the Shiraiwa and Fujino's model was used to calculate characteristic intensities and scattering interactions. This model makes certain assumptions and approximations to achieve the calculations, especially in the case of the geometrical conditions and the incident and take-off beams. For the binary sample studied in this work and the considered experimental conditions, the calculations show that the resonant Raman scattering background is significant under the fluorescent peak, affects the symmetry of the peaks and, depending on the concentrations, overcomes the enhancements contributions (secondary fluorescence).

  5. X-ray excitation fluorescence spectra of the Eu2+-stabilized VK center in alkaline-earth fluoride mixed-crystal systems

    NASA Astrophysics Data System (ADS)

    Kawano, K.; Ohya, T.; Tsurumi, T.; Katoh, K.; Nakata, R.

    1999-11-01

    X-ray excitation fluorescence spectra were investigated for MF2:Eu (M=Ca, Sr, and Ba) and their mixed-crystal systems, Ca1-xSrxF2 and Sr1-xBaxF2 with the same fluorite structure. The UV recombination fluorescence band of the VK center associated with blue emission due to the f-d transition of Eu2+ ions was observed with changing mixture ratios x at room temperature. Two sets of weak spectra due to f-f transitions of Eu3+ ions also appeared in the 500-600-nm wavelength region. The peak wavelengths and the integrated intensities of the observed fluorescence were investigated as a function of the Eu concentration as well as the mixture ratio. For the blue emission of Eu2+, pulsed x-ray excitation resulted in shorter lifetimes (500-800 ns) than optical excitation, suggesting energy transfers between the excited states of VK centers and Eu2+. A kinematical fluorescence mechanism was proposed, taking into account the formation of a close pair of a hopping VK center and an immobile Eu2+ ion followed by an energy transfer from the former to the latter. Based on the calculated fluorescence decay curves best fitted to the response curves by x-ray pulse excitation, the energy transfer rates from VK centers to Eu2+ were estimated.

  6. Unexpected solvent effects on the UV/Vis absorption spectra of o-cresol in toluene and benzene: in contrast with non-aromatic solvents

    PubMed Central

    Zheng, Dong; Yuan, Xiang-Ai; Ma, Haibo; Li, Xiaoxiong; Wang, Xizhang; Liu, Ziteng

    2018-01-01

    Cresol is a prototype molecule in understanding intermolecular interactions in material and biological systems, because it offers different binding sites with various solvents and protonation states under different pH values. It is found that the UV/Vis absorption spectra of o-cresol in aromatic solvents (benzene, toluene) are characterized by a sharp peak, unlike the broad double-peaks in 11 non-aromatic solvents. Both molecular dynamics simulations and electronic structure calculations revealed the formation of intermolecular π-complexation between o-cresol and aromatic solvents. The thermal movements of solvent and solute molecules render the conformations of o-cresol changing between trans and cis isomers. The π-interaction makes the cis configuration a dominant isomer, hence leading to the single keen-edged UV/Vis absorption peak at approximately 283 nm. The free conformation changes between trans and cis in aqueous solution rationalize the broader absorption peaks in the range of 260–280 nm. The pH dependence of the UV/Vis absorption spectra in aqueous solutions is also rationalized by different protonation states of o-cresol. The explicit solvent model with long-ranged interactions is vital to describe the effects of π-complexation and electrostatic interaction on the UV/Vis absorption spectra of o-cresol in toluene and alkaline aqueous (pH > 10.3) solutions, respectively. PMID:29657794

  7. Unexpected solvent effects on the UV/Vis absorption spectra of o-cresol in toluene and benzene: in contrast with non-aromatic solvents.

    PubMed

    Zheng, Dong; Yuan, Xiang-Ai; Ma, Haibo; Li, Xiaoxiong; Wang, Xizhang; Liu, Ziteng; Ma, Jing

    2018-03-01

    Cresol is a prototype molecule in understanding intermolecular interactions in material and biological systems, because it offers different binding sites with various solvents and protonation states under different pH values. It is found that the UV/Vis absorption spectra of o -cresol in aromatic solvents (benzene, toluene) are characterized by a sharp peak, unlike the broad double-peaks in 11 non-aromatic solvents. Both molecular dynamics simulations and electronic structure calculations revealed the formation of intermolecular π-complexation between o -cresol and aromatic solvents. The thermal movements of solvent and solute molecules render the conformations of o -cresol changing between trans and cis isomers. The π-interaction makes the cis configuration a dominant isomer, hence leading to the single keen-edged UV/Vis absorption peak at approximately 283 nm. The free conformation changes between trans and cis in aqueous solution rationalize the broader absorption peaks in the range of 260-280 nm. The pH dependence of the UV/Vis absorption spectra in aqueous solutions is also rationalized by different protonation states of o -cresol. The explicit solvent model with long-ranged interactions is vital to describe the effects of π-complexation and electrostatic interaction on the UV/Vis absorption spectra of o -cresol in toluene and alkaline aqueous (pH > 10.3) solutions, respectively.

  8. Collision-Induced Absorption Spectra of Binary Mixtures of Molecular Hydrogen with Molecular Deuterium and Argon and of Pure Hydrogen, D

    NASA Astrophysics Data System (ADS)

    Hsieh, Chang-Tsang William

    In the present research project a systematic study of the collision-induced infrared absorption (CIA) spectra of the binary mixtures of H_2 - D_2 in the region of the double fundamental vibrations of H_2 and D_2, and H_2 - Ar in the fundamental band of H_2, and of pure HD in its fundamental and first overtone regions was undertaken. The experiments were carried out with a 2.0 m high-pressure low-temperature transmission-type absorption cell at 77, 201 and 296 K at total gas densities up to 550 amagat. Infrared prism and grating spectrometers equipped with a microprocessor -controlled stepping motor were used to record the spectra. All the experimental results obtained represent first-time observations in collision-induced absorption. Collision-induced infrared absorption spectra of the double transitions of H_2(v=1>=ts 0) and D_2(v=1>=ts 0) have been observed at 77 and 201 K in the spectral region 7000-8000 cm^{-1} for total gas densities up to 550 amagat with a partial gas density ratio of 1:1 of H_2 and D_2. The observed spectra are interpreted in terms of the transitions, Q_1(J) of H_2+Q_1(J) of D _2, Q_1(J) of H_2+S _1(J) of D_2, S_1(J) of H_2 + Q_1(J) of D_2, and S_1(J) of H_2 + S_1(J) of D_2 for J = 0 and 1 for H _2 and J = 0, 1, and 2 for D_2. Analysis of the experimental absorption profiles was carried out using appropriate lineshape functions. The absorption coefficients, lineshape parameters, etc., are obtained from the analysis. Collision-induced enhancement absorption spectra of the fundamental band of H_2 in H_2 - Ar mixtures were recorded at room temperature for a base density of 72 amagat of H_2 for several partial densities of Ar up to 440 amagat. Hexadecapole-induced U transitions, U_1(1), U_1(2), Q_1(0)+U _0(1), and Q_1(1) + U_0(1) have been identified in the spectral region 5400 -6200 cm^{-1}. A "cage" model has been proposed to account for the double transitions of H_2 - H_2 in the H _2 - Ar enhancement spectra. From the analysis of the

  9. Interactions of hemin with bovine serum albumin and human hemoglobin: A fluorescence quenching study.

    PubMed

    Makarska-Bialokoz, Magdalena

    2018-03-15

    The binding interactions between hemin (Hmi) and bovine serum albumin (BSA) or human hemoglobin (HHb), respectively, have been examined in aqueous solution at pH=7.4, applying UV-vis absorption, as well as steady-state, synchronous and three-dimensional fluorescence spectra techniques. Representative results received for both BSA and HHb intrinsic fluorescence proceeding from the interactions with hemin suggest the formation of stacking non-covalent and non-fluorescent complexes in both the Hmi-BSA and Hmi-HHb systems, with highly possible concurrent formation of a coordinate bond between a group on the protein surface and the metal in Hmi molecule. All the values of calculated parameters, the binding, fluorescence quenching and bimolecular quenching rate constants point to the involvement of static quenching in both the systems studied. The blue shift in the synchronous fluorescence spectra imply the participation of both tryptophan and tyrosine residues in quenching of BSA and HHb intrinsic fluorescence. Depicted outcomes suggest that hemin is supposedly able to influence the physiological functions of BSA and HHb, the most important blood proteins, particularly in case of its overuse. Copyright © 2017 Elsevier B.V. All rights reserved.

  10. Absorption and fluorescence properties of chromophoric dissolved organic matter: implications for the monitoring of water quality in a large subtropical reservoir.

    PubMed

    Liu, Xiaohan; Zhang, Yunlin; Shi, Kun; Zhu, Guangwei; Xu, Hai; Zhu, Mengyuan

    2014-12-01

    The development of techniques for real-time monitoring of water quality is of great importance for effectively managing inland water resources. In this study, we first analyzed the absorption and fluorescence properties in a large subtropical reservoir and then used a chromophoric dissolved organic matter (CDOM) fluorescence monitoring sensor to predict several water quality parameters including the total nitrogen (TN), total phosphorus (TP), chemical oxygen demand (COD), dissolved organic carbon (DOC), and CDOM fluorescence parallel factor analysis (PARAFAC) components in the reservoir. The CDOM absorption coefficient at 254 nm (a(254)), the humic-like component (C1), and the tryptophan-like component (C3) decreased significantly along a gradient from the northwest to the lake center, northeast, southwest, and southeast region in the reservoir. However, no significant spatial difference was found for the tyrosine-like component (C2), which contributed only four marked peaks. A highly significant linear correlation was found between the a(254) and CDOM concentration measured using the CDOM fluorescence sensor (r(2) = 0.865, n = 76, p < 0.001), indicating that CDOM concentrations could act as a proxy for the CDOM absorption coefficient measured in the laboratory. Significant correlations were also found between the CDOM concentration and TN, TP, COD, DOC, and the maximum fluorescence intensity of C1, suggesting that the real-time monitoring of CDOM concentrations could be used to predict these water quality parameters and trace the humic-like fluorescence substance in clear aquatic ecosystems with DOC <2 mg/L and total suspended matter (TSM) concentrations <15 mg/L. These results demonstrate that the CDOM fluorescence sensor is a useful tool for on-line water quality monitoring if the empirical relationship between the CDOM concentration measured using the CDOM fluorescence sensor and the water quality parameters is calibrated and validated.

  11. Predicting the Shifts of Absorption Maxima of Azulene Derivatives Using Molecular Modeling and ZINDO CI Calculations of UV-Vis Spectra

    ERIC Educational Resources Information Center

    Patalinghug, Wyona C.; Chang, Maharlika; Solis, Joanne

    2007-01-01

    The deep blue color of azulene is drastically changed by the addition of substituents such as CH[subscript 3], F, or CHO. Computational semiempirical methods using ZINDO CI are used to model azulene and azulene derivatives and to calculate their UV-vis spectra. The calculated spectra are used to show the trends in absorption band shifts upon…

  12. Quantification of optical absorption coefficient from acoustic spectra in the optical diffusive regime using photoacoustic microscopy

    NASA Astrophysics Data System (ADS)

    Guo, Zijian; Favazza, Christopher; Wang, Lihong V.

    2012-02-01

    Photoacoustic (PA) tomography (PAT) can image optical absorption contrast with ultrasonic spatial resolution in the optical diffusive regime. Multi-wavelength PAT can noninvasively monitor hemoglobin oxygen saturation (sO2) with high sensitivity and fine spatial resolution. However, accurate quantification in PAT requires knowledge of the optical fluence distribution, acoustic wave attenuation, and detection system bandwidth. We propose a method to circumvent this requirement using acoustic spectra of PA signals acquired at two optical wavelengths. With the acoustic spectral method, the absorption coefficients of an oxygenated bovine blood phantom at 560 and 575 nm were quantified with errors of ><5%.

  13. Determination of K shell absorption jump factors and jump ratios of 3d transition metals by measuring K shell fluorescence parameters.

    PubMed

    Kaçal, Mustafa Recep; Han, İbrahim; Akman, Ferdi

    2015-01-01

    Energy dispersive X-ray fluorescence technique (EDXRF) has been employed for measuring K-shell absorption jump factors and jump ratios for Ti, Cr, Fe, Co, Ni and Cu elements. The jump factors and jump ratios for these elements were determined by measuring K shell fluorescence parameters such as the Kα X-ray production cross-sections, K shell fluorescence yields, Kβ-to-Kα X-rays intensity ratios, total atomic absorption cross sections and mass attenuation coefficients. The measurements were performed using a Cd-109 radioactive point source and an Si(Li) detector in direct excitation and transmission experimental geometry. The measured values for jump factors and jump ratios were compared with theoretically calculated and the ones available in the literature. Copyright © 2014 Elsevier Ltd. All rights reserved.

  14. Theoretical design and investigation of 1,8-naphthalimide-based two-photon fluorescent probes for detecting cytochrome P450 1A with separated fluorescence signal.

    PubMed

    Zhang, Chun; Ren, Ai-Min; Guo, Jing-Fu; Wang, Dan; Yu, Li-Ying

    2018-05-16

    As a type of enzyme with a terminal oxygen, the CYP1A subfamily possesses the ability to catalyze the reactions of many environmental toxins, endogenous substrates and clinical drugs. The development of efficient methods for the rapid and real-time detection of CYP1A enzyme activity in complex biological systems is of considerable significance for identifying potential abnormalities in these cancer-related enzymes. With this goal, we firstly provided a series of 1,8-naphthalimide-based two-photon fluorescent chromophores with large two-photon absorption (TPA) cross-sections (500-7000 GM) and remarkable changes in fluorescence spectra upon recognizing the CYP1A enzyme from its theoretical aspect. Moreover, we have thoroughly studied the effects of cyclic acceptor (dichlorobenzene and benzothiadiazole) and donor (fluorene and carbazole) groups on the one-photon absorption (OPA), TPA, and fluorescence properties of CYP1A enzyme probes and the corresponding reaction products. The connection of a heterocycle as the donor group to a 1,8-naphthalimide-based molecule to form a D-π-A-π-D-type electronic structure can effectively cause red shifts in the absorption and emission wavelengths to facilitate bioimaging in the near infrared (NIR) region, which is attributed to the lower transition energy, larger transition dipole moment and amount of transferred charge. Docking analysis suggests that the two-photon fluorescent probes NCMN-3 and NCMN-5 that were designed will guarantee and achieve excellent selectivity for the CYP1A enzyme.

  15. Measuring partial fluorescence yield using filtered detectors.

    PubMed

    Boyko, T D; Green, R J; Moewes, A; Regier, T Z

    2014-07-01

    Typically, X-ray absorption near-edge structure measurements aim to probe the linear attenuation coefficient. These measurements are often carried out using partial fluorescence yield techniques that rely on detectors having photon energy discrimination improving the sensitivity and the signal-to-background ratio of the measured spectra. However, measuring the partial fluorescence yield in the soft X-ray regime with reasonable efficiency requires solid-state detectors, which have limitations due to the inherent dead-time while measuring. Alternatively, many of the available detectors that are not energy dispersive do not suffer from photon count rate limitations. A filter placed in front of one of these detectors will make the energy-dependent efficiency non-linear, thereby changing the responsivity of the detector. It is shown that using an array of filtered X-ray detectors is a viable method for measuring soft X-ray partial fluorescence yield spectra without dead-time. The feasibility of this technique is further demonstrated using α-Fe2O3 as an example and it is shown that this detector technology could vastly improve the photon collection efficiency at synchrotrons and that these detectors will allow experiments to be completed with a much lower photon flux reducing X-ray-induced damage.

  16. Fluorine Kα X-Ray Emission Spectra of MgF2, CaF2, SrF2 and BaF2

    NASA Astrophysics Data System (ADS)

    Sugiura, Chikara; Konishi, Wataru; Shoji, Shizuko; Kojima, Shinjiro

    1990-11-01

    The fluorine Kα emission spectra in fluorescence from a series of alkaline-earth fluorides MF2 (M=Mg, Ca, Sr and Ba) are measured with a high-resolution two-crystal vacuum spectrometer. An anomalously low intensity of the K1L1 satellite peak arising from 1s-1(2s2p)-1 initial states is observed for SrF2. The measured emission spectra are presented along with the UPS spectra of the F- 2p valence bands obtained by Poole et al. and the fluorine K absorption-edge spectra by Oizumi et al. By using these spectra, the first peak or shoulder in the fluorine K absorption-edge spectra is identified as being due to a core exciton which is formed below the bottom of the conduction band. The binding energy of the exciton is estimated to be 1.3(± 0.3), 1.1(± 0.2), 1.0(± 0.2) and 1.7(± 0.2) eV for MgF2, CaF2, SrF2 and BaF2, respectively.

  17. Wavelet based de-noising of breath air absorption spectra profiles for improved classification by principal component analysis

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

    The comparison results of different mother wavelets used for de-noising of model and experimental data which were presented by profiles of absorption spectra of exhaled air are presented. The impact of wavelets de-noising on classification quality made by principal component analysis are also discussed.

  18. The P K-near edge absorption spectra of phosphates

    NASA Astrophysics Data System (ADS)

    Franke, R.; Hormes, J.

    1995-12-01

    The X-ray absorption near edge structure (XANES) at the P K-edge in several orthophosphates with various cations, in condensed, and in substituted sodium phosphates have been measured using synchrotron radiation from the ELSA storage ring at the University of Bonn. The measured spectra demonstrate that chemical changes beyond the PO 4- tetrahedra are reflected by energy shifts of the pre-edge and continuum resonances, by the presence of characteristic shoulders and new peaks and by differences in the intensity of the white line. We discuss the energy differences between the white line positions and the corresponding P ls binding energies as a measure of half of the energy gap. The corresponding values correlate with the valence of the cations and the intensity of the white lines. The energy positions of the continuum resonances are discussed on the basis of an empirical bond-length correlation supporting a 1/ r2 - dependence.

  19. Substituent and solvent effects on the UV/Vis absorption spectra of 5-(4-substituted arylazo)-6-hydroxy-4-methyl-3-cyano-2-pyridones

    NASA Astrophysics Data System (ADS)

    Ušćumlić, Gordana S.; Mijin, Dusanˇ Z. ˇ; Valentić, Nataša V.; Vajs, Vlatka V.; Sušić, Biljana M.

    2004-10-01

    Absorption spectra of ten 5-(4-substituted arylazo)-6-hydroxy-4-methyl-3-cyano-2-pyridones have been recorded in fifteen solvents in the range 200-600 nm. The substituents at the phenyl nucleus are as follows: OH, OCH 3, CH 3, C 2H 5, H, Cl, Br, I, COOH and NO 2. The effects of substituents on the absorption spectra of investigated compounds are interpreted by correlation of absorption frequencies with simple Hammett equation. The effects of solvent polarity and solvent/solute hydrogen bonding interactions are analyzed by means of linear solvation energy relationships concept proposed by Kamlet and Taft. The azo-hydrazone tuatomeric equilibration is found to depend upon substituents as well as on solvents.

  20. Changes in fluorescence spectra of bioaerosols exposed to ozone in a laboratory reaction chamber to simulate atmospheric aging.

    PubMed

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

    2012-12-31

    A laboratory system for exposing aerosol particles to ozone and rapidly measuring the subsequent changes in their single-particle fluorescence is reported. The system consists of a rotating drum chamber and a single-particle fluorescence spectrometer (SPFS) utilizing excitation at 263 nm. Measurements made with this system show preliminary results on the ultra-violet laser-induced-fluorescence (UV-LIF) spectra of single aerosolized particles of Yersinia rohdei, and of MS2 (bacteriophage) exposed to ozone. When bioparticles are exposed in the chamber the fluorescence emission peak around 330 nm: i) decreases in intensity relative to that of the 400-550 nm band; and ii) shifts slightly toward shorter-wavelengths (consistent with further drying of the particles). In these experiments, changes were observed at exposures below the US Environmental Protection Agency (EPA) limits for ozone.

  1. Fluorescence Spectroscopy Applied to Monitoring Biodiesel Degradation: Correlation with Acid Value and UV Absorption Analyses.

    PubMed

    Vasconcelos, Maydla Dos Santos; Passos, Wilson Espíndola; Lescanos, Caroline Honaiser; Pires de Oliveira, Ivan; Trindade, Magno Aparecido Gonçalves; Caires, Anderson Rodrigues Lima; Muzzi, Rozanna Marques

    2018-01-01

    The techniques used to monitor the quality of the biodiesel are intensely discussed in the literature, partly because of the different oil sources and their intrinsic physicochemical characteristics. This study aimed to monitor the thermal degradation of the fatty acid methyl esters of Sesamum indicum L. and Raphanus sativus L. biodiesels (SILB and RSLB, resp.). The results showed that both biodiesels present a high content of unsaturated fatty acids, ∼84% (SILB) and ∼90% (RSLB). The SILB had a high content of polyunsaturated linoleic fatty acid (18  :  2), about 49%, and the oleic monounsaturated (18  :  1), ∼34%. On the other hand, RSLB presented a considerable content of linolenic fatty acid (18  :  3), ∼11%. The biodiesel samples were thermal degraded at 110°C for 48 hours, and acid value, UV absorption, and fluorescence spectroscopy analysis were carried out. The results revealed that both absorption and fluorescence presented a correlation with acid value as a function of degradation time by monitoring absorptions at 232 and 270 nm as well as the emission at 424 nm. Although the obtained correlation is not completely linear, a direct correlation was observed in both cases, revealing that both properties can be potentially used for monitoring the biodiesel degradation.

  2. [Fluorescence spectra and quantum yield of TiO2 nanocrystals synthesized by alcohothermal method].

    PubMed

    Song, Cui-Hong; Li, Yan-Ting; Li, Jing; Wei, Yong-Ju; Hu, Yu-Zhu; Wei, Yu

    2008-01-01

    Fluorescence spectra and fluorescence quantum yield of TiO2 nanocrystals were studied. Using tetra n-butyl titanate as a starting material, a facile alcohothermal technique was used to synthesize TiO2 nanocrystals. As can be seen from the transmittance electron microscopy (TEM) image, TiO2 nanocrystals with a relatively uniform particle size distribution of < 10 nm are present in the transparent sol. The transparent sol presents a strong stable fluorescence emission with a maximum at 450 nm, which is greatly dependent on the size quantization effects, defect energy level and the surface state of TiO2 nanocrystals. The quantum yield (gamma) of TiO2 was determined by the relative comparison procedure, using freshly prepared analytical purity quinine sulfate in 0.05 mol x L(-1) H2SO4 as a relative quantum yield standard. The emission quantum yield of TiO2 nanocrystals prepared in alcoholic media was calculated to be about 0.20 at wavelengths ranging from 330 to 370 nm, which was much higher than the values reported in previous works. So, it is supposed that nano-TiO2 will be applied as a potential quantum dots fluorescence probe in biological analysis.

  3. Artifact suppression in electron paramagnetic resonance imaging of 14N- and 15N-labeled nitroxyl radicals with asymmetric absorption spectra

    NASA Astrophysics Data System (ADS)

    Takahashi, Wataru; Miyake, Yusuke; Hirata, Hiroshi

    2014-10-01

    This article describes an improved method for suppressing image artifacts in the visualization of 14N- and 15N-labeled nitroxyl radicals in a single image scan using electron paramagnetic resonance (EPR). The purpose of this work was to solve the problem of asymmetric EPR absorption spectra in spectral processing. A hybrid function of Gaussian and Lorentzian lineshapes was used to perform spectral line-fitting to successfully separate the two kinds of nitroxyl radicals. This approach can process the asymmetric EPR absorption spectra of the nitroxyl radicals being measured, and can suppress image artifacts due to spectral asymmetry. With this improved visualization method and a 750-MHz continuous-wave EPR imager, a temporal change in the distributions of a two-phase paraffin oil and water/glycerin solution system was visualized using lipophilic and hydrophilic nitroxyl radicals, i.e., 2-(14-carboxytetradecyl)-2-ethyl-4,4-dimethyl-3-oxazolidinyloxy (16-DOXYL stearic acid) and 4-hydroxyl-2,2,6,6-tetramethylpiperidine-d17-1-15N-1-oxyl (TEMPOL-d17-15N). The results of the two-phase separation experiment verified that reasonable artifact suppression could be achieved by the present method that deals with asymmetric absorption spectra in the EPR imaging of 14N- and 15N-labeled nitroxyl radicals.

  4. K β X-Ray Emission Spectra of Phosphorus Oxo Acids and Anions

    NASA Astrophysics Data System (ADS)

    Sugiura, Chikara

    1995-03-01

    With a high-resolution two-crystal vacuum spectrometer, the phosphorus Kβ emission spectra in fluorescence are measured for H3PO3 (= H2PHO3), H3PO4, Li3PO4, Na3PO4·12H2O, Na2HPO4, NaH2PO4, K3PO4·nH2O, K2HPO4, KH2PO4, Ca3(PO4)2, CaHPO4·2H2O, Ca(H2PO4)2·H2O, CaHPO3·H2O, Ca(H2PO2)2 and NH4H2PO4. In the phosphate compounds, a weak peak is observed on the high-energy side of the main peak Kβ1 and related to a molecular orbital of t2 symmetry in the PO43- ion. It is shown that the phosphorus Kβ emission spectra are influenced by ligand substitution and cations. The measured Kβ emission spectra of Li3PO4, Na3PO4·12H2O, K3PO4·nH2O and Ca3(PO4)2 are presented along with the previously reported P-K absorption spectra of these phosphate compounds. The emission and absorption spectra are interpreted in terms of available molecular orbitals of the PO43- ion.

  5. Detection of intaoral lesions using a fluorescence camera

    NASA Astrophysics Data System (ADS)

    Thoms, Michael

    2006-02-01

    Optical methods for the detection of carious lesions, calculus and plaque have the advantage of being minimally invasive. The use of endogeneous fluorescence markers like porphyrins could simplify the application of fluorescence techniques in the dental practice. It is known that porphyrins are produced by some of the bacterial species that are present in the oral cavity. Since porphyrins have an excitation band at about 400nm they have the potential to be used as fluorescent markers of locations in the oral cavity where the production of bacteria is out of the limits of healthy regions. Further, modern and efficient GaN-based semiconductor diodes emit light in this spectral range and thus make the implementation of fluorescence sensors with excitation at this wavelength easy. Carious lesions, calculus and plaque have been measured using a self build fluorescence camera using GaN-diodes for illumination at 405nm. Further, emission spectra under this excitation were recorded. For the latter purpose freshly extracted teeth were used. It has been found that already in the case of an initial carious lesion red porphyrin-fluorescence is emitted whereas it is absent in healthy enamel. In already brown coloured carious lesions the emission bands of porphyrin are present but the observed overall fluorescence intensity is lower, probably due to the absorption of the fluorescence by the carious defect itself. In dental calculus, dental plaque and subgingival concrements porphyrin originated luminescence was found as well. Since in these cases the emission spectra differ slightly it can be concluded that they originate from different types of porphyrins and thus also from different bacteria. These results show that this fluorescence technique can be a promising method to diagnose carious lesions, calculus and plaque.

  6. Determining CDOM Absorption Spectra in Diverse Coastal Environments Using a Multiple Pathlength, Liquid Core Waveguide System. Measuring the Absorption of CDOM in the Field Using a Multiple Pathlength Liquid Waveguide System

    NASA Technical Reports Server (NTRS)

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

    2000-01-01

    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, a(sub CDOM), 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 (r > 0.99) and showed a linear response across all four pathlengths. Values of a(sub CDOM) measured using the MPLCW were virtually identical to spectrophotometer values over a wide range of concentrations. The dynamic range of a(sub CDOM) for MPLCW measurements was 0.002 - 231.5/m. At low CDOM concentrations (a(sub 370) < 0.1/m) spectrophotometric a(sub CDOM) 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. The maximum deviation in replicate MPLCW spectra was less than 0.001 absorbance units. The portability, sampling, and optical characteristics of a MPLCW system provide significant enhancements for routine CDOM absorption measurements in a broad range of natural waters.

  7. Calculation of Transfer Functions of Multilayer Biotissues in the Problems of Correction of Their Fluorescence Spectra

    NASA Astrophysics Data System (ADS)

    Lysenko, S. A.

    2018-01-01

    A method for rapid calculation of a flux of stimulated fluorescence of a multilayer optically dense medium with inhomogeneous distribution of the fluorophore has been developed. The light field in the medium at the excitation wavelength of fluorescence is represented by a superposition of incident collimated, incident diffuse, and reflected diffuse fluxes. A two-stream approximation is used to describe the light field in the medium at the wavelength of emission of the fluorescence. Fluxes in adjacent elementary layers of the medium and on its surface are connected by simple matrix operators that are obtained using a combination of engineering approaches of radiation-transfer theory and single-scattering approximation. The calculations of fluorescence fluxes of a four-layer biotissue that are excited and recorded at 400-800 nm are compared with their Monte Carlo simulation with a discrepancy of 1%. The effect of the propagation medium on the fluorescence spectra of 5-ALA-induced protoporphyrin IX that are recorded from human skin was studied, and a technique for their correction that is based on measurements and quantitative analysis of the diffuse reflectance spectrum of skin was proposed.

  8. 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.

  9. Interaction of thioflavin T with amyloid fibrils: stoichiometry and affinity of dye binding, absorption spectra of bound dye.

    PubMed

    Sulatskaya, Anna I; Kuznetsova, Irina M; Turoverov, Konstantin K

    2011-10-06

    The fluorescence of the benzothiazole dye thioflavin T (ThT) is a well-known test for amyloid fibril formation. It has now become evident that ThT can also be used for structural investigations of amyloid fibrils and even for the treatment of amyloid diseases. In this case, one of the most urgent problems is an accurate determination of ThT-amyloid fibril binding parameters: the number of binding modes, stoichiometry, and binding constant for each mode. To obtain information concerning the ThT-amyloid fibril binding parameters, we propose to use absorption spectrophotometry of solutions prepared by equilibrium microdialysis. This approach is inherently designed for the determination of dye-receptor binding parameters. However, it has been very rarely used in the study of dye-protein interactions and has never been used to study the binding parameters of ThT or its analogues to amyloid fibrils. We showed that, when done in corpore, this approach enables the determination of not only binding parameters but also the absorption spectrum and molar extinction coefficient of ThT bound to sites of different binding modes. The proposed approach was used for the examination of lysozyme amyloid fibrils. Two binding modes were found for the ThT-lysozyme amyloid fibril interaction. These binding modes have significantly different binding constants (K(b1) = 7.5 × 10(6) M(-1), K(b2) = 5.6 × 10(4) M(-1)) and a different number of dye binding sites on the amyloid fibrils per protein molecule (n(1) = 0.11, n(2) = 0.24). The absorption spectra of ThT bound to sites of different modes differ from each other (ε(b1,max) = 5.1 × 10(4) M(-1) cm(-1), ε(b2,max) = 6.7 × 10(4) M(-1)cm(-1), λ(max) = 449 nm) and significantly differ from that of free ThT in aqueous solution (ε(max) = 3.2 × 10(4) M(-1)cm(-1), λ(max) = 412 nm). © 2011 American Chemical Society

  10. Enhanced 1.32 μm fluorescence and broadband amplifying for O-band optical amplifier in Nd3+-doped tellurite glass

    NASA Astrophysics Data System (ADS)

    Zhou, Zi-zhong; Zhou, Ming-han; Su, Xiu-e.; Cheng, Pan; Zhou, Ya-xun

    2017-01-01

    WO3 oxides with relatively high phonon energy and different concentrations were introduced into the Nd3+-doped tellurite-based glasses of TeO2-ZnO-Na2O to improve the 1.32 μm band fluorescence emission. The absorption spectra, Raman spectra, 1.32 μm band fluorescence spectra and differential scanning calorimeter (DSC) curves were measured, together with the Judd-Ofelt intensity parameters, stimulated emission and gain parameters were calculated to evaluate the effects of WO3 amount on the glass structure and spectroscopic properties of 1.32 μm band fluorescence. It is shown that the introduction of an appropriate amount of WO3 oxide can effectively improve the 1.32 μm band fluorescence intensity through the enhanced multi-phonon relaxation (MPR) processes between the excited levels of Nd3+. The results indicate that the prepared Nd3+-doped tellurite glass with an appropriate amount of WO3 oxide is a potential gain medium applied for the O-band broad and high-gain fiber amplifier.

  11. Serial Femtosecond Crystallography and Ultrafast Absorption Spectroscopy of the Photoswitchable Fluorescent Protein IrisFP.

    PubMed

    Colletier, Jacques-Philippe; Sliwa, Michel; Gallat, François-Xavier; Sugahara, Michihiro; Guillon, Virginia; Schirò, Giorgio; Coquelle, Nicolas; Woodhouse, Joyce; Roux, Laure; Gotthard, Guillaume; Royant, Antoine; Uriarte, Lucas Martinez; Ruckebusch, Cyril; Joti, Yasumasa; Byrdin, Martin; Mizohata, Eiichi; Nango, Eriko; Tanaka, Tomoyuki; Tono, Kensuke; Yabashi, Makina; Adam, Virgile; Cammarata, Marco; Schlichting, Ilme; Bourgeois, Dominique; Weik, Martin

    2016-03-03

    Reversibly photoswitchable fluorescent proteins find growing applications in cell biology, yet mechanistic details, in particular on the ultrafast photochemical time scale, remain unknown. We employed time-resolved pump-probe absorption spectroscopy on the reversibly photoswitchable fluorescent protein IrisFP in solution to study photoswitching from the nonfluorescent (off) to the fluorescent (on) state. Evidence is provided for the existence of several intermediate states on the pico- and microsecond time scales that are attributed to chromophore isomerization and proton transfer, respectively. Kinetic modeling favors a sequential mechanism with the existence of two excited state intermediates with lifetimes of 2 and 15 ps, the second of which controls the photoswitching quantum yield. In order to support that IrisFP is suited for time-resolved experiments aiming at a structural characterization of these ps intermediates, we used serial femtosecond crystallography at an X-ray free electron laser and solved the structure of IrisFP in its on state. Sample consumption was minimized by embedding crystals in mineral grease, in which they remain photoswitchable. Our spectroscopic and structural results pave the way for time-resolved serial femtosecond crystallography aiming at characterizing the structure of ultrafast intermediates in reversibly photoswitchable fluorescent proteins.

  12. Design, properties and application of a facile fluorescence switch for Cu(II).

    PubMed

    Diao, Haipeng; Niu, Weiping; Liu, Wen; Feng, Liheng; Xie, Jun

    2017-01-05

    A facile fluorescence switch based on Schiff base 2,2'-[1,3-phenylenbis- (methylidynenitrilo)]bis[benzenethiol] (PMBB) has been developed and used to sensing metal ions. UV-vis absorption and fluorescence emission spectra show that the PMBB receptor has high selectivity and sensitivity for Cu(II) ions. Based on the photoinduced electron transfer (PET) and chelation enhanced fluorescence (CHEF) mechanisms, the receptor exhibits an fluorescence "turn-on" switch signal for Cu(II). The 1:1 binding mode of PMBB and Cu (II) ions can be obtained by the Job-plot and ESI-Mass spectra data. Noticeably, the color changes (from colorless to yellow) of PMBB solutions for Cu(II) sensing can be observed by naked eyes in the sunlight. The detection limit of the receptor for Cu(II) may reach 10(-7)mol/L with a good linear relation in the lower concentrations of Cu(II). To develop the practical application, the Cu(II) ions in swimming pool water samples were detected. Results show that PMBB receptor as a fluorescent probe can use to detect the trace level of Cu(II) in the environmental samples. This work contributes to providing a facile strategy for designing efficient probes and developing their practical application value. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. 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.

  14. UV-Vis absorption spectra and electronic structure of merocyanines in the gas phase

    NASA Astrophysics Data System (ADS)

    Ishchenko, Alexander A.; Kulinich, Andrii V.; Bondarev, Stanislav L.; Raichenok, Tamara F.

    2018-02-01

    Gas-phase absorption spectra of a merocyanine vinylogous series have been studied for the first time. In vapour, their long-wavelength absorption bands were found to be considerably shifted hypsochromically, broader, more symmetrical, less intense, and their vinylene shift much smaller than even in low-polarity n-hexane. This indicates that in the gas phase their electronic structure closely approaches the nonpolar polyene limiting structure. The TDDFT calculations of the long-wavelength electronic transitions in the studied merocyanines in vacuo demonstrated good-to-excellent correlation - depending on the functional used - with the obtained experimental data. For comparison, the solvent effects was accounted for using the polarizable continuum model (PCM) with n-hexane and ethanol as low-polarity and high-polarity media, and compared with the UV-Vis spectral data in these solvents. In this case, the discrepancy between theory and experiment was much greater, increasing at that with the polymethine chain length.

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

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

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

  16. Correlation fluorescence method of amine detection

    NASA Astrophysics Data System (ADS)

    Myslitsky, Valentin F.; Tkachuk, Svetlana S.; Rudeichuk, Volodimir M.; Strinadko, Miroslav T.; Slyotov, Mikhail M.; Strinadko, Marina M.

    1997-12-01

    The amines fluorescence spectra stimulated by UV laser radiation are investigated in this paper. The fluorescence is stimulated by the coherent laser beam with the wavelength 0.337 micrometers . At the sufficient energy of laser stimulation the narrow peaks of the fluorescence spectra are detected besides the wide maximum. The relationship between the fluorescence intensity and the concentration of amines solutions are investigated. The fluorescence intensity temporal dependence on wavelength 0.363 micrometers of the norepinephrine solution preliminarily radiated by UV laser with wavelength 0.337 micrometers was found. The computer stimulated and experimental investigations of adrenaline and norepinephrine mixtures fluorescence spectra were done. The correlation fluorescent method of amines detection is proposed.

  17. Temperature dependence of the optical absorption spectra of InP/ZnS quantum dots

    NASA Astrophysics Data System (ADS)

    Savchenko, S. S.; Vokhmintsev, A. S.; Weinstein, I. A.

    2017-03-01

    The optical-absorption spectra of InP/ZnS (core/shell) quantum dots have been studied in a broad temperature range of T = 6.5-296 K. Using the second-order derivative spectrophotometry technique, the energies of optical transitions at room temperature were found to be E 1 = 2.60 ± 0.02 eV (for the first peak of excitonic absorption in the InP core) and E 2 = 4.70 ± 0.02 eV (for processes in the ZnS shell). The experimental curve of E 1( T) has been approximated for the first time in the framework of a linear model and in terms of the Fan's formula. It is established that the temperature dependence of E 1 is determined by the interaction of excitons and longitudinal acoustic phonons with hω = 15 meV.

  18. 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.

  19. On the origin of a very close similarity between the spectra of the supernova type 1 in NGC 3198 and the absorption of DQ HeR

    NASA Technical Reports Server (NTRS)

    Mustel, E. R.

    1979-01-01

    The type 1 supernova discovered late in 1966 in NGC 3198 has broad minima in its spectrum break down into a number of significantly narrower absorption bands. The broad minima of tau, sigma and mu, which usually show no details in the spectra of type supernovas, contain a number of narrow absorption bands. The reality of most of these absorption bands is demonstrated by comparison of recordings of spectra of the supernova presented for two moments in time. These minima (particularly of tau and mu,) are a result of blending of several broad absorption bands. The minimum of tau should be a blend of intensive and very broad Fe absorption lines, in which the lower level is metastable. The wavelengths of these line are: 5169, 5198, 5235, 5276, 5317, 5363A.

  20. Modeling techniques and fluorescence imaging investigation of the interactions of an anthraquinone derivative with HSA and ctDNA

    NASA Astrophysics Data System (ADS)

    Fu, Zheng; Cui, Yanrui; Cui, Fengling; Zhang, Guisheng

    2016-01-01

    A new anthraquinone derivative (AORha) was synthesized. Its interactions with human serum albumin (HSA) and calf thymus DNA (ctDNA) were investigated by fluorescence spectroscopy, UV-visible absorption spectroscopy and molecular modeling. Cell viability assay and cell imaging experiment were performed using cervical cancer cells (HepG2 cells). The fluorescence results revealed that the quenching mechanism was static quenching. At different temperatures (290, 300, 310 K), the binding constants (K) and the number of binding sites (n) were determined, respectively. The positive ΔH and ΔS values showed that the binding of AORha with HSA was hydrophobic force, which was identical with the molecular docking result. Studying the fluorescence spectra, UV spectra and molecular modeling also verified that the binding mode of AORha and ctDNA might be intercalative. When HepG2 cells were treated with AORha, the fluorescence became brighter and turned green, which could be used for bioimaging.

  1. Modeling techniques and fluorescence imaging investigation of the interactions of an anthraquinone derivative with HSA and ctDNA.

    PubMed

    Fu, Zheng; Cui, Yanrui; Cui, Fengling; Zhang, Guisheng

    2016-01-15

    A new anthraquinone derivative (AORha) was synthesized. Its interactions with human serum albumin (HSA) and calf thymus DNA (ctDNA) were investigated by fluorescence spectroscopy, UV-visible absorption spectroscopy and molecular modeling. Cell viability assay and cell imaging experiment were performed using cervical cancer cells (HepG2 cells). The fluorescence results revealed that the quenching mechanism was static quenching. At different temperatures (290, 300, 310 K), the binding constants (K) and the number of binding sites (n) were determined, respectively. The positive ΔH and ΔS values showed that the binding of AORha with HSA was hydrophobic force, which was identical with the molecular docking result. Studying the fluorescence spectra, UV spectra and molecular modeling also verified that the binding mode of AORha and ctDNA might be intercalative. When HepG2 cells were treated with AORha, the fluorescence became brighter and turned green, which could be used for bioimaging. Copyright © 2015 Elsevier B.V. All rights reserved.

  2. Absorption, fluorescence and second harmonic generation in Cr3+-doped BiB3O6 glasses

    NASA Astrophysics Data System (ADS)

    Kuznik, W.; Fuks-Janczarek, I.; Wojciechowski, A.; Kityk, I. V.; Kiisk, V.; Majchrowski, A.; Jaroszewicz, L. R.; Brik, M. G.; Nagy, G. U. L.

    2015-06-01

    Synthesis, spectral properties and photoinduced nonlinear optical effects of chromium-doped BiB3O6 glass are studied in the present paper. Absorption, excitation and time resolved luminescence spectra are presented and luminescence decay behavior is discussed. Detailed analysis of the obtained spectra (assignment of the most prominent spectral features in terms of the corresponding Cr3+ energy levels, crystal field strength Dq, Racah parameters B and C) was performed. A weak photostimulated second harmonic generation signal was found to increase drastically due to poling by proton implantation in the investigated sample.

  3. [Electronic spectra of triphenodioxazines dyes by modified PPP-MO method].

    PubMed

    Wang, Xue-jie

    2002-02-01

    The triphenodioxazines dyes have good colour and luster, excellent colour fastness to light, and strong painted. They are used as the dyes and pigment extensively, and also be used as the photoelectronic transformation, laser dyes and far-infrared anti-radiation material. The colour and constitution of triphenodioxazines dyes were evaluated by means of the modified PPP-SCF-MO method with variable R, beta approximation. The calculated wavelengths of maximum absorption are in good agreement with experimental results. It was found that there exists a good correlated relationship between the wavenumber of fluorescence maximum nu fl and the calculated fluorescence emission energy delta Efl, as nu fl = 11.6837 delta Efl + 3.3485(k.cm-1), r = 0.9547. The relationship between structure of molecular and properties of electronic spectra has been discussed.

  4. Path integral Monte Carlo study on the structure and absorption spectra of alkali atoms (Li, Na, K) attached to superfluid helium clusters

    NASA Astrophysics Data System (ADS)

    Nakayama, Akira; Yamashita, Koichi

    2001-01-01

    Path integral Monte Carlo calculations have been performed to investigate the microscopic structure and thermodynamic properties of the AkṡHeN (Ak=Li, Na, K,N⩽300) clusters at T=0.5 K. Absorption spectra which correspond to the 2P←2S transitions of alkali atoms are also calculated within a pairwise additive model, which employs diatomic Ak-He potential energy curves. The size dependences of the cluster structure and absorption spectra that show the influence of the helium cluster environment are examined in detail. It is found that alkali atoms are trapped in a dimple on the helium cluster's surface and that, from the asymptotic behavior, the AkṡHe300 cluster, at least semiquantitatively, mimics the local structure of experimentally produced large helium clusters in the vicinity of alkali atoms. We have successfully reproduced the overall shapes of the spectra and explained their features from a static and structural point of view. The positions, relative intensities, and line widths of the absorption maxima are calculated to be in moderate agreement with experiments [F. Stienkemeier, J. Higgins, C. Callegari, S. I. Kanorsky, W. E. Ernst, and G. Scoles, Z. Phys. D 38, 253 (1996)].

  5. The effect of annulation of benzene rings on the photophysics and electronic structure of tetraazachlorin molecules

    NASA Astrophysics Data System (ADS)

    Pershukevich, P. P.; Volkovich, D. I.; Gladkov, L. L.; Dudkin, S. V.; Kuzmitsky, V. A.; Makarova, E. A.; Solovyev, K. N.

    2017-10-01

    The photophysics and electronic structure of tribenzotetraazachlorins (H2, Zn, and Mg), which are novel analogues of phtalocyanines, have been studied experimentally and theoretically. At 293 K, the electronic absorption, fluorescence, and fluorescence excitation spectra are recorded and the fluorescence quantum yield and lifetime, as well as the quantum yield of singlet oxygen generation, are measured; at 77 K, the fluorescence, fluorescence excitation, and fluorescence polarization spectra are recorded and the fluorescence lifetime values are measured. The dependences of the absorption spectra and photophysical parameters on the structure variation are analyzed in detail. Quantum-chemical calculations of the electronic structure and absorption spectra of tribenzotetraazachlorins (H2, Mg) are performed using the INDO/Sm method (modified INDO/S method) based on molecular-geometry optimization by the DFT PBE/TZVP method. The results of quantum-chemical calculations of the electronic absorption spectra are in very good agreement with the experimental data for the transitions to two lower electronic states.

  6. Absorption and emission behaviour of trans- p-coumaric acid in aqueous solutions and some organic solvents

    NASA Astrophysics Data System (ADS)

    Putschögl, M.; Zirak, P.; Penzkofer, A.

    2008-01-01

    The absorption and fluorescence behaviour of trans- p-coumaric acid ( trans-4-hydroxycinnamic acid) is investigated in buffered aqueous solution over a wide range from pH 1 to pH 12, in un-buffered water, and in some organic solvents. Absorption cross-section spectra, fluorescence quantum distributions, fluorescence quantum yields, and degrees of fluorescence polarisation are measured. p-Coumaric acid exists in different ionic forms in aqueous solution depending on the pH. There is an equilibrium between the neutral form ( p-CAH 2) and the single anionic form ( p-CAH -) at low pH (p Kna ≈ 4.9), and between the single anionic and the double anionic form ( p-CA 2-) at high pH (p Kaa ≈ 9.35). In the organic solvents studied trans- p-coumaric acid is dissolved in its neutral form. The fluorescence quantum yield of trans- p-coumaric acid in aqueous solution is ϕF ≈ 1.4 × 10 -4 for the neutral and the single anionic form, while it is ϕF ≈ 1.3 × 10 -3 for the double anionic form. For trans- p-coumaric acid in organic solvents fluorescence quantum yields in the range from 4.8 × 10 -5 (acetonitrile) to 1.5 × 10 -4 (glycerol) were measured. The fluorescence spectra are 7700-10,000 cm -1 Stokes shifted in aqueous solution, and 5400-8200 cm -1 Stokes shifted in the studied organic solvents. Decay paths responsible for the low fluorescence quantum yields are discussed (photo-isomerisation and internal conversion for p-CA 2-, solvent-assisted intra-molecular charge-transfer or ππ ∗ to nπ ∗ transfer and internal conversion for p-CAH 2 and p-CAH -). The solvent dependence of the first ππ ∗ electronic transition frequency and of the fluorescence Stokes shift of p-CAH 2 is discussed in terms of polar solute-solvent interaction effects. Thereby the ground-state and excite-state molecular dipole moments are extracted.

  7. A simple approach to spectrally resolved fluorescence and bright field microscopy over select regions of interest

    NASA Astrophysics Data System (ADS)

    Dahlberg, Peter D.; Boughter, Christopher T.; Faruk, Nabil F.; Hong, Lu; Koh, Young Hoon; Reyer, Matthew A.; Shaiber, Alon; Sherani, Aiman; Zhang, Jiacheng; Jureller, Justin E.; Hammond, Adam T.

    2016-11-01

    A standard wide field inverted microscope was converted to a spatially selective spectrally resolved microscope through the addition of a polarizing beam splitter, a pair of polarizers, an amplitude-mode liquid crystal-spatial light modulator, and a USB spectrometer. The instrument is capable of simultaneously imaging and acquiring spectra over user defined regions of interest. The microscope can also be operated in a bright-field mode to acquire absorption spectra of micron scale objects. The utility of the instrument is demonstrated on three different samples. First, the instrument is used to resolve three differently labeled fluorescent beads in vitro. Second, the instrument is used to recover time dependent bleaching dynamics that have distinct spectral changes in the cyanobacteria, Synechococcus leopoliensis UTEX 625. Lastly, the technique is used to acquire the absorption spectra of CH3NH3PbBr3 perovskites and measure differences between nanocrystal films and micron scale crystals.

  8. A simple approach to spectrally resolved fluorescence and bright field microscopy over select regions of interest.

    PubMed

    Dahlberg, Peter D; Boughter, Christopher T; Faruk, Nabil F; Hong, Lu; Koh, Young Hoon; Reyer, Matthew A; Shaiber, Alon; Sherani, Aiman; Zhang, Jiacheng; Jureller, Justin E; Hammond, Adam T

    2016-11-01

    A standard wide field inverted microscope was converted to a spatially selective spectrally resolved microscope through the addition of a polarizing beam splitter, a pair of polarizers, an amplitude-mode liquid crystal-spatial light modulator, and a USB spectrometer. The instrument is capable of simultaneously imaging and acquiring spectra over user defined regions of interest. The microscope can also be operated in a bright-field mode to acquire absorption spectra of micron scale objects. The utility of the instrument is demonstrated on three different samples. First, the instrument is used to resolve three differently labeled fluorescent beads in vitro. Second, the instrument is used to recover time dependent bleaching dynamics that have distinct spectral changes in the cyanobacteria, Synechococcus leopoliensis UTEX 625. Lastly, the technique is used to acquire the absorption spectra of CH 3 NH 3 PbBr 3 perovskites and measure differences between nanocrystal films and micron scale crystals.

  9. Two-Photon Absorption Spectroscopy of Rubidium with a Dual-Comb Tequnique

    NASA Astrophysics Data System (ADS)

    Nishiyama, Akiko; Yoshida, Satoru; Hariki, Takuya; Nakajima, Yoshiaki; Minoshima, Kaoru

    2017-06-01

    Dual-comb spectroscopies have great potential for high-resolution molecular and atomic spectroscopies, thanks to the broadband comb spectrum consisting of dense narrow modes. In this study, we apply the dual-comb system to Doppler-free two-photon absorption spectroscopy. The outputs of two frequency combs excite several two-photon transitions of rubidium, and we obtained broadband Doppler-free spectra from dual-comb fluorescence signals. The fluorescence detection scheme circumvents the sensitivity limit which is effectively determined by the dynamic range of photodetectors in absorption-based dual-comb spectroscopies. Our system realized high-sensitive, Doppler-free high-resolution and broadband atomic spectroscopy. A part of observed spectra of 5S_{1/2} - 5D_{5/2} transition is shown in the figure. The hyperfine structures of the F" = 1 - F' = 3,2,1 transitions are fully-resolved and the spectral widths are approximately 5 MHz. The absolute frequency axis is precisely calibrated from comb mode frequencies which were stabilized to a GPS-disciplined clock. This work was supported by JST through the ERATO MINOSHIMA Intelligent Optical Synthesizer Project and Grant-in-Aid for JSPS Fellows (16J02345). A. Nishiyama, S. Yoshida, Y. Nakajima, H. Sasada, K. Nakagawa, A. Onae, K. and Minoshima, Opt. Express 24, 25894 (2016). A. Hipke, S. A. Meek, T. Ideguchi, T.W. Hänsch, and N. Picqué, Phys. Rev. A 90, 011805(R) (2014).

  10. 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. Copyright © 2011 Elsevier Ltd. All rights reserved.

  11. Laser induced fluorescence and phosphorescence of matrix isolated glyoxal - Evidence for exciplex formation in the A 1Au and a 3Au states

    NASA Technical Reports Server (NTRS)

    Van Ijzendoorn, L. J.; Baas, F.; Koernig, S.; Greenberg, J. M.; Allamandola, L. J.

    1986-01-01

    Laser-induced fluorescence and phosphorescence as well as infrared and visible absorption spectra of glyoxal in Ar, N2, and CO matrices are presented and analyzed. Glyoxal in its first excited electronic state is shown to form an exciplex with its nearest neighbors in all three matrices, and transitions normally forbidden dominate the emission spectra. The spectral characteristics of these complexes are similar to those of the Ar-glyoxal complex found in supersonic beam experiments. Due to the matrix cage effect, no vibrational predissociation is observed. The phosphorescence lifetime is determined and an upper limit is given for the fluorescence lifetime. This, in combination with the relative intensities of fluorescence and phosphorescence, can be used to place limits on the quantum yields of the various relaxation processes.

  12. Transition metal atomic multiplets in the ligand K-edge x-ray absorption spectra and multiple oxidation states in the L2,3 emission of strongly correlated compounds

    NASA Astrophysics Data System (ADS)

    Jiménez-Mier, J.; Olalde-Velasco, P.; Yang, W.-L.; Denlinger, J.

    2014-07-01

    We present results that show that atomic multiplet ligand field calculations are in very good agreement with experimental x-ray absorption spectra at the L2,3 edge of transition metal (TM) di-fluorides (MF2, MCrCu). For chromium more than one TM oxidation state is needed to achieve such an agreement. We also show that signature of the TM atomic multiplet can be found at the pre-edge of the fluorine K-edge x-ray absorption spectra. TM atomic multiplet ligand field calculations with a structureless core hole show good agreement with the observed pre-edges in the experimental fluorine absorption spectra. Preliminary results for the comparison between calculated and experimental resonant x-ray emission spectra for nominal CrF2 with more than one oxidation state indicate the presence of three chromium oxidation states in the bulk.

  13. Relativistic Effects on Reflection X-ray Spectra of AGN

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lee, Khee-Gan; /University Coll. London; Fuerst, Steven V.

    2007-01-05

    We have calculated the reflection component of the X-ray spectra of active galactic nuclei (AGN) and shown that they can be significantly modified by the relativistic motion of the accretion flow and various gravitational effects of the central black hole. The absorption edges in the reflection spectra suffer severe energy shifts and smearing. The degree of distortion depends on the system parameters, and the dependence is stronger for some parameters such as the inner radius of the accretion disk and the disk viewing inclination angles. The relativistic effects are significant and are observable. Improper treatment of the reflection component ofmore » the X-ray continuum in spectral fittings will give rise to spurious line-like features, which will mimic the fluorescent emission lines and mask the relativistic signatures of the lines.« less

  14. XAS spectroelectrochemistry: reliable measurement of X-ray absorption spectra from redox manipulated solutions at room temperature.

    PubMed

    Best, Stephen P; Levina, Aviva; Glover, Chris; Johannessen, Bernt; Kappen, Peter; Lay, Peter A

    2016-05-01

    The design and operation of a low-volume spectroelectrochemical cell for X-ray absorption spectroscopy (XAS) of solutions at room temperature is described. Fluorescence XAS measurements are obtained from samples contained in the void space of a 50 µL reticulated vitreous carbon (sponge) working electrode. Both rapid electrosynthesis and control of the effects of photoreduction are achieved by control over the flow properties of the solution through the working electrode, where a good balance between the rate of consumption of sample and the minimization of decomposition was obtained by pulsing the flow of the solution by 1-2 µL with duty cycle of ∼3 s while maintaining a small net flow rate (26-100 µL h(-1)). The performance of the cell in terms of control of the redox state of the sample and minimization of the effects of photoreduction was demonstrated by XAS measurements of aqueous solutions of the photosensitive Fe(III) species, [Fe(C2O4)3](3-), together with that of the electrogenerated [Fe(C2O4)3](4-) product. The current response from the cell during the collection of XAS spectra provides an independent measure of the stability of the sample of the measurement. The suitability of the approach for the study of small volumes of mM concentrations of protein samples was demonstrated by the measurement of the oxidized and electrochemically reduced forms of cytochrome c.

  15. Quantification of Material Fluorescence and Light Scattering Cross Sections Using Ratiometric Bandwidth-Varied Polarized Resonance Synchronous Spectroscopy.

    PubMed

    Xu, Joanna Xiuzhu; Hu, Juan; Zhang, Dongmao

    2018-05-25

    Presented herein is the ratiometric bandwidth-varied polarized resonance synchronous spectroscopy (BVPRS2) method for quantification of material optical activity spectra. These include the sample light absorption and scattering cross-section spectrum, the scattering depolarization spectrum, and the fluorescence emission cross-section and depolarization spectrum in the wavelength region where the sample both absorbs and emits. This ratiometric BVPRS2 spectroscopic method is a self-contained technique capable of quantitatively decoupling material fluorescence and light scattering signal contribution to its ratiometric BVPRS2 spectra through the linear curve-fitting of the ratiometric BVPRS2 signal as a function of the wavelength bandwidth used in the PRS2 measurements. Example applications of this new spectroscopic method are demonstrated with materials that can be approximated as pure scatterers, simultaneous photon absorbers/emitters, simultaneous photon absorbers/scatterers, and finally simultaneous photon absorbers/scatterers/emitters. Because the only instruments needed for this ratiometric BVPRS2 technique are the conventional UV-vis spectrophotometer and spectrofluorometer, this work should open doors for routine decomposition of material UV-vis extinction spectrum into its absorption and scattering component spectra. The methodology and insights provided in this work should be of broad significance to all chemical research that involves photon/matter interactions.

  16. Determination of rice syrup adulterant concentration in honey using three-dimensional fluorescence spectra and multivariate calibrations

    NASA Astrophysics Data System (ADS)

    Chen, Quansheng; Qi, Shuai; Li, Huanhuan; Han, Xiaoyan; Ouyang, Qin; Zhao, Jiewen

    2014-10-01

    To rapidly and efficiently detect the presence of adulterants in honey, three-dimensional fluorescence spectroscopy (3DFS) technique was employed with the help of multivariate calibration. The data of 3D fluorescence spectra were compressed using characteristic extraction and the principal component analysis (PCA). Then, partial least squares (PLS) and back propagation neural network (BP-ANN) algorithms were used for modeling. The model was optimized by cross validation, and its performance was evaluated according to root mean square error of prediction (RMSEP) and correlation coefficient (R) in prediction set. The results showed that BP-ANN model was superior to PLS models, and the optimum prediction results of the mixed group (sunflower ± longan ± buckwheat ± rape) model were achieved as follow: RMSEP = 0.0235 and R = 0.9787 in the prediction set. The study demonstrated that the 3D fluorescence spectroscopy technique combined with multivariate calibration has high potential in rapid, nondestructive, and accurate quantitative analysis of honey adulteration.

  17. Isomers in the excited state of electron-transferring flavoprotein from Megasphaera elsdenii: spectral resolution from the time-resolved fluorescence spectra.

    PubMed

    Sato, Kyosuke; Nishina, Yasuzo; Shiga, Kiyoshi; Tanaka, Fumio

    2008-02-27

    Electron-transferring flavoprotein (Holo-ETF) from Megasphaera elsdenii contains two FAD's, one of which easily dissociates to form Iso-ETF (contains one FAD). Time-resolved fluorescence of FAD in Iso-ETF, and Holo-ETF were measured at 5 degrees C and 25 degrees C. Wavelength-dependent fluorescence decays of the both ETF at 5 degrees C and 25 degrees C were analyzed to resolve them into two independent spectra. It was found that Iso-ETF displayed two spectra with lifetime of 0.605 ns (emission peak, 508 nm) and with lifetime of 1.70 ns (emission peak, 540 nm) at 5 degrees C, and with lifetime of 0.693 ns (emission peak, 508 nm) and with lifetime of 2.75 ns (emission peak, 540 nm) at 25 degrees C. Holo-ETF displayed two spectra with lifetime of 0.739 ns (emission peak, 508 nm) and with lifetime of 2.06 ns (emission peak, 545 nm) at 5 degrees C, and with lifetime of 0.711 ns (emission peak, 527 nm) and with lifetime of 3.08 ns (emission peak, 540 nm) at 25 degrees C. Thus fluorescence lifetimes of every spectrum increased upon elevating temperature. Emission peaks Iso-ETF did not change much upon elevating temperature. Activation enthalpy changes, activation entropy changes and activation Gibbs energy changes of quenching rates all displayed negative. Two emission species in the both ETF may be hydrogen-bonding isomers, because isoalloxazine ring of FAD contains four hydrogen acceptors and one donor.

  18. Photoabsorption of green and red fluorescent protein chromophore anions in vacuo.

    PubMed

    Wan, Songbo; Liu, Shasha; Zhao, Guangjiu; Chen, Maodu; Han, Keli; Sun, Mengtao

    2007-09-01

    Photoabsorption properties of green and red fluorescent protein chromophore anions in vacuo were investigated theoretically, based on the experimental results in gas phase [Phys. Rev. Lett. 2001, 87, 228102; Phys. Rev. Lett. 2003, 90, 118103]. Their calculated transition energies in absorption with TD-DFT and ZINDO methods are directly compared to the experimental reports in gas phase, and the calculations with ZINDO method can correctly reproduce the absorption spectra. The orientation and strength of their transition dipole moments were revealed with transition density. We also showed the orientation and result of their intramolecular charge transfer with transition difference density. The calculated results show that with the increase of the extended conjugated system, the orientation of transition dipole moments and the orientation of charge transfer can be reversed. They are the linear responds with the external electric fields. These theoretical results reveal the insight understanding of the photoinduced dynamics of green and red fluorescent protein chromophore anions and cations in vacuo.

  19. Ground-based Photon Path Measurements from Solar Absorption Spectra of the O2 A-band

    NASA Technical Reports Server (NTRS)

    Yang, Z.; Wennberg, P. O.; Cageao, R. P.; Pongetti, T. J.; Toon, G. C.; Sander, S. P.

    2005-01-01

    High-resolution solar absorption spectra obtained from Table Mountain Facility (TMF, 34.38degN, 117.68degW, 2286 m elevation) have been analyzed in the region of the O2 A-band. The photon paths of direct sunlight in clear sky cases are retrieved from the O2 absorption lines and compared with ray-tracing calculations based on the solar zenith angle and surface pressure. At a given zenith angle, the ratios of retrieved to geometrically derived photon paths are highly precise (approx.0.2%), but they vary as the zenith angle changes. This is because current models of the spectral lineshape in this band do not properly account for the significant absorption that exists far from the centers of saturated lines. For example, use of a Voigt function with Lorentzian far wings results in an error in the retrieved photon path of as much as 5%, highly correlated with solar zenith angle. Adopting a super-Lorentz function reduces, but does not completely eliminate this problem. New lab measurements of the lineshape are required to make further progress.

  20. Combined thioflavin T-Congo red fluorescence assay for amyloid fibril detection

    NASA Astrophysics Data System (ADS)

    Girych, Mykhailo; Gorbenko, Galyna; Maliyov, Ivan; Trusova, Valeriya; Mizuguchi, Chiharu; Saito, Hiroyuki; Kinnunen, Paavo

    2016-09-01

    Fluorescence represents one of the most powerful tools for the detection and structural characterization of the pathogenic protein aggregates, amyloid fibrils. The traditional approaches to the identification and quantification of amyloid fibrils are based on monitoring the fluorescence changes of the benzothiazole dye thioflavin T (ThT) and absorbance changes of the azo dye Congo red (CR). In routine screening it is usually sufficient to perform only the ThT and CR assays, but both of them, when used separately, could give false results. Moreover, fibrillization kinetics can be measured only by ThT fluorescence, while the characteristic absorption spectra and birefringence of CR represent more rigid criteria for the presence of amyloid fibrils. Therefore, it seemed reasonable to use both these dyes simultaneously, combining the advantages of each technique. To this end, we undertook a detailed analysis of the fluorescence spectral behavior of these unique amyloid tracers upon their binding to amyloid fibrils from lysozyme, insulin and an N-terminal fragment of apolipoprotein A-I with Iowa mutation. The fluorescence measurements revealed several criteria for distinguishing between fibrillar and monomeric protein states: (i) a common drastic increase in ThT fluorescence intensity; (ii) a sharp decrease in ThT fluorescence upon addition of CR; (iii) an appearance of the maximum at 535-540 nm in the CR excitation spectra; (iv) increase in CR fluorescence intensity at 610 nm. Based on these findings we designed a novel combined ThT-CR fluorescence assay for amyloid identification. Such an approach not only strengthens the reliability of the ThT assay, but also provides new opportunities for structural characterization of amyloid fibrils.

  1. Double-Resonance Facilitated Decomposion of Emission Spectra

    NASA Astrophysics Data System (ADS)

    Kato, Ryota; Ishikawa, Haruki

    2016-06-01

    Emission spectra provide us with rich information about the excited-state processes such as proton-transfer, charge-transfer and so on. In the cases that more than one excited states are involved, emission spectra from different excited states sometimes overlap and a decomposition of the overlapped spectra is desired. One of the methods to perform a decomposition is a time-resolved fluorescence technique. It uses a difference in time evolutions of components involved. However, in the gas-phase, a concentration of the sample is frequently too small to carry out this method. On the other hand, double-resonance technique is a very powerful tool to discriminate or identify a common species in the spectra in the gas-phase. Thus, in the present study, we applied the double-resonance technique to resolve the overlapped emission spectra. When transient IR absorption spectra of the excited state are available, we can label the population of the certain species by the IR excitation with a proper selection of the IR wavenumbers. Thus, we can obtain the emission spectra of labeled species by subtracting the emission spectra with IR labeling from that without IR. In the present study, we chose the charge-transfer emission spectra of cyanophenyldisilane (CPDS) as a test system. One of us reported that two charge-transfer (CT) states are involved in the intramolecular charge-transfer (ICT) process of CPDS-water cluster and recorded the transient IR spectra. As expected, we have succeeded in resolving the CT emission spectra of CPDS-water cluster by the double resonance facilitated decomposion technique. In the present paper, we will report the details of the experimental scheme and the results of the decomposition of the emission spectra. H. Ishikawa, et al., Chem. Phys. Phys. Chem., 9, 117 (2007).

  2. Improved discrimination between monocotyledonous and dicotyledonous plants for weed control based on the blue-green region of ultraviolet-induced fluorescence spectra.

    PubMed

    Panneton, Bernard; Guillaume, Serge; Roger, Jean-Michel; Samson, Guy

    2010-01-01

    Precision weeding by spot spraying in real time requires sensors to discriminate between weeds and crop without contact. Among the optical based solutions, the ultraviolet (UV) induced fluorescence of the plants appears as a promising alternative. In a first paper, the feasibility of discriminating between corn hybrids, monocotyledonous, and dicotyledonous weeds was demonstrated on the basis of the complete spectra. Some considerations about the different sources of fluorescence oriented the focus to the blue-green fluorescence (BGF) part, ignoring the chlorophyll fluorescence that is inherently more variable in time. This paper investigates the potential of performing weed/crop discrimination on the basis of several large spectral bands in the BGF area. A partial least squares discriminant analysis (PLS-DA) was performed on a set of 1908 spectra of corn and weed plants over 3 years and various growing conditions. The discrimination between monocotyledonous and dicotyledonous plants based on the blue-green fluorescence yielded robust models (classification error between 1.3 and 4.6% for between-year validation). On the basis of the analysis of the PLS-DA model, two large bands were chosen in the blue-green fluorescence zone (400-425 nm and 425-490 nm). A linear discriminant analysis based on the signal from these two bands also provided very robust inter-year results (classification error from 1.5% to 5.2%). The same selection process was applied to discriminate between monocotyledonous weeds and maize but yielded no robust models (up to 50% inter-year error). Further work will be required to solve this problem and provide a complete UV fluorescence based sensor for weed-maize discrimination.

  3. Robust and economical multi-sample, multi-wavelength UV/vis absorption and fluorescence detector for biological and chemical contamination

    NASA Astrophysics Data System (ADS)

    Lu, Peter J.; Hoehl, Melanie M.; Macarthur, James B.; Sims, Peter A.; Ma, Hongshen; Slocum, Alexander H.

    2012-09-01

    We present a portable multi-channel, multi-sample UV/vis absorption and fluorescence detection device, which has no moving parts, can operate wirelessly and on batteries, interfaces with smart mobile phones or tablets, and has the sensitivity of commercial instruments costing an order of magnitude more. We use UV absorption to measure the concentration of ethylene glycol in water solutions at all levels above those deemed unsafe by the United States Food and Drug Administration; in addition we use fluorescence to measure the concentration of d-glucose. Both wavelengths can be used concurrently to increase measurement robustness and increase detection sensitivity. Our small robust economical device can be deployed in the absence of laboratory infrastructure, and therefore may find applications immediately following natural disasters, and in more general deployment for much broader-based testing of food, agricultural and household products to prevent outbreaks of poisoning and disease.

  4. Pixel-based absorption correction for dual-tracer fluorescence imaging of receptor binding potential

    PubMed Central

    Kanick, Stephen C.; Tichauer, Kenneth M.; Gunn, Jason; Samkoe, Kimberley S.; Pogue, Brian W.

    2014-01-01

    Ratiometric approaches to quantifying molecular concentrations have been used for decades in microscopy, but have rarely been exploited in vivo until recently. One dual-tracer approach can utilize an untargeted reference tracer to account for non-specific uptake of a receptor-targeted tracer, and ultimately estimate receptor binding potential quantitatively. However, interpretation of the relative dynamic distribution kinetics is confounded by differences in local tissue absorption at the wavelengths used for each tracer. This study simulated the influence of absorption on fluorescence emission intensity and depth sensitivity at typical near-infrared fluorophore wavelength bands near 700 and 800 nm in mouse skin in order to correct for these tissue optical differences in signal detection. Changes in blood volume [1-3%] and hemoglobin oxygen saturation [0-100%] were demonstrated to introduce substantial distortions to receptor binding estimates (error > 30%), whereas sampled depth was relatively insensitive to wavelength (error < 6%). In response, a pixel-by-pixel normalization of tracer inputs immediately post-injection was found to account for spatial heterogeneities in local absorption properties. Application of the pixel-based normalization method to an in vivo imaging study demonstrated significant improvement, as compared with a reference tissue normalization approach. PMID:25360349

  5. 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.

  6. Laser-Induced Photofragmentation Fluorescence Imaging of Alkali Compounds in Flames.

    PubMed

    Leffler, Tomas; Brackmann, Christian; Aldén, Marcus; Li, Zhongshan

    2017-06-01

    Laser-induced photofragmentation fluorescence has been investigated for the imaging of alkali compounds in premixed laminar methane-air flames. An ArF excimer laser, providing pulses of wavelength 193 nm, was used to photodissociate KCl, KOH, and NaCl molecules in the post-flame region and fluorescence from the excited atomic alkali fragment was detected. Fluorescence emission spectra showed distinct lines of the alkali atoms allowing for efficient background filtering. Temperature data from Rayleigh scattering measurements together with simulations of potassium chemistry presented in literature allowed for conclusions on the relative contributions of potassium species KOH and KCl to the detected signal. Experimental approaches for separate measurements of these components are discussed. Signal power dependence and calculated fractions of dissociated molecules indicate the saturation of the photolysis process, independent on absorption cross-section, under the experimental conditions. Quantitative KCl concentrations up to 30 parts per million (ppm) were evaluated from the fluorescence data and showed good agreement with results from ultraviolet absorption measurements. Detection limits for KCl photofragmentation fluorescence imaging of 0.5 and 1.0 ppm were determined for averaged and single-shot data, respectively. Moreover, simultaneous imaging of KCl and NaCl was demonstrated using a stereoscope with filters. The results indicate that the photofragmentation method can be employed for detailed studies of alkali chemistry in laboratory flames for validation of chemical kinetic mechanisms crucial for efficient biomass fuel utilization.

  7. Using of laser spectroscopy and chemometrics methods for identification of patients with lung cancer, patients with COPD and healthy people from absorption spectra of exhaled air

    NASA Astrophysics Data System (ADS)

    Bukreeva, Ekaterina B.; Bulanova, Anna A.; Kistenev, Yury V.; Kuzmin, Dmitry A.; Nikiforova, Olga Yu.; Ponomarev, Yurii N.; Tuzikov, Sergei A.; Yumov, Evgeny L.

    2014-11-01

    The results of application of the joint use of laser photoacoustic spectroscopy and chemometrics methods in gas analysis of exhaled air of patients with chronic respiratory diseases (chronic obstructive pulmonary disease and lung cancer) are presented. The absorption spectra of exhaled breath of representatives of the target groups and healthy volunteers were measured; the selection by chemometrics methods of the most informative absorption coefficients in scan spectra in terms of the separation investigated nosology was implemented.

  8. Spectral and Fluorescent Studies of the Interaction of an Anionic Oxacarbocyanine Dye with Bovine Serum Albumin

    NASA Astrophysics Data System (ADS)

    Pronkin, P. G.; Tatikolov, A. S.

    2017-01-01

    The influence of the formation of noncovalent intermolecular complexes with bovine serum albumin (BSA) on the spectral and fluorescent properties of the anionic oxacarbocyanine dye 3,3'-di-(γ-sulfopropyl)-5,5'-diphenyl-9-ethyloxacarbocyanine betaine (OCC) was studied. Binding of OCC to BSA increased significantly the dye fluorescence. Changes in the absorption and fluorescence spectra of OCC upon interaction with BSA argued in favor of a shift of the dye cis-trans equilibrium in the complex. The effects of adding albumin-denaturing compounds (urea, sodium dodecyl sulfate) on the spectral and fluorescent properties of the dye in the OCC-BSA complex were studied. It was concluded that OCC can act as a probe for albumins and can be used to study protein denaturing.

  9. Studies on interaction of an intramolecular charge transfer fluorescence probe: 4'-dimethylamino-2,5-dihydroxychalcone with DNA.

    PubMed

    Xu, Zhicheng; Bai, Guan; Dong, Chuan

    2005-10-15

    The interaction of a new intramolecular charge transfer probe, namely 4'-dimethylamino-2,5-dihydroxychalcone (DMADHC), with calf thymus DNA has been studied. Compared to the spectral characteristics of the free form in aqueous solution, the fluorescence of DMADHC enhanced dramatically accompanying a blueshift of the emission maxima in the presence of DNA. The absorption and fluorescence spectra, salt concentration effect, KI quenching, fluorescence polarization, and DNA denaturation experiments were given. These results give evidence that the DMADHC molecule is inserted into the base-stacking domain of the DNA double helix. The intrinsic binding constant and the binding site number were estimated. The analytical characteristics were also given.

  10. The influence of surface plasmons on fluorescence of the dye Lumogen F red 300 in condensed phase

    NASA Astrophysics Data System (ADS)

    Reisfeld, Renata; Levchenko, Viktoria

    2017-01-01

    The paper is divided to two parts one is a short description of scientific activity of Georges Boulon and my long standing friendship with him, the second part consists of the new findings of increasing fluorescence by surface plasmons studies performed recently in Jerusalem. We describe the synthesis of copper nanoparticles and their incorporation into polyvinylpyrrolidone and into sol-gel matrix co-doped with the fluorescent dye Lumogen F Red 300. The absorption and emission spectra of samples undoped and co-doped with nanoparticles reveal the increase of fluorescence of the dye in presence of copper nanoparticles. The phenomenon arises from scattered light by the nanoparticles.

  11. Interaction of a dinuclear fluorescent Cd(II) complex of calix[4]arene conjugate with phosphates and its applicability in cell imaging.

    PubMed

    Sreenivasu Mummidivarapu, V V; Hinge, Vijaya Kumar; Rao, Chebrolu Pulla

    2015-01-21

    A triazole-linked hydroxyethylimino conjugate of calix[4]arene () and its cadmium complex have been synthesized and characterized, and their structures have been established. In the complex, both the Cd(2+) centers are bound by an N2O4 core, and one of it is a distorted octahedral, whereas the other is a trigonal anti-prism. The fluorescence intensity of the di-nuclear Cd(ii) complex is quenched only in the presence of phosphates and not with other anions studied owing to their binding affinities and the nature of the interaction of the phosphates with Cd(2+). These are evident even from their absorption spectra. Different phosphates exhibit changes in both their fluorescence as well as absorption spectra to varying extents, suggesting their differential interactions. Among the six phosphates, H2PO4(-) has higher fluorescence quenching even at low equivalents of this ion, whereas P2O7(4-) shows only 50% quenching even at 10 equivalents. The fluorescence quenching is considerable even at 20 ppb (0.2 μM) of H2PO4(-), whereas all other phosphates require a concentration of 50-580 ppb to exhibit the same effect on fluorescence spectra. Thus, the interaction of H2PO4(-) is more effective by ∼30 fold as compared to that of P2O7(4-). Fluorescence quenching by phosphate is due to the release of from its original cadmium complex via the formation of a ternary species followed by the capture of Cd(2+) by the phosphate, as delineated based on the combination of spectral techniques, such as absorption, emission, (1)H NMR and ESI MS. The relative interactive abilities of the six phosphates differ from each other. The removal of Cd(2+) is demonstrated to be reversible by the repeated addition of the phosphate followed by Cd(2+). The characteristics of the ternary species formed in each of these six phosphates have been computationally modeled using molecular mechanics. The computational study revealed that the coordination between cadmium and -CH2-CH2-OH breaks and new

  12. Probe pressure effects on human skin diffuse reflectance and fluorescence spectroscopy measurements

    PubMed Central

    Lim, Liang; Nichols, Brandon; Rajaram, Narasimhan; Tunnell, James W.

    2011-01-01

    Diffuse reflectance and fluorescence spectroscopy are popular research techniques for noninvasive disease diagnostics. Most systems include an optical fiber probe that transmits and collects optical spectra in contact with the suspected lesion. The purpose of this study is to investigate probe pressure effects on human skin spectroscopic measurements. We conduct an in-vivo experiment on human skin tissue to study the short-term (<2 s) and long-term (>30 s) effects of probe pressure on diffuse reflectance and fluorescence measurements. Short-term light probe pressure (P0 < 9 mN∕mm2) effects are within 0 ± 10% on all physiological properties extracted from diffuse reflectance and fluorescence measurements, and less than 0 ± 5% for diagnostically significant physiological properties. Absorption decreases with site-specific variations due to blood being compressed out of the sampled volume. Reduced scattering coefficient variation is site specific. Intrinsic fluorescence shows a large standard error, although no specific pressure-related trend is observed. Differences in tissue structure and morphology contribute to site-specific probe pressure effects. Therefore, the effects of pressure can be minimized when the pressure is small and applied for a short amount of time; however, long-term and large pressures induce significant distortions in measured spectra. PMID:21280899

  13. Vibrationally high-resolved electronic spectra of MCl2 (M=C, Si, Ge, Sn, Pb) and photoelectron spectra of MCl2(.).

    PubMed

    Ran, Yibin; Pang, Min; Shen, Wei; Li, Ming; He, Rongxing

    2016-10-05

    We systematically studied the vibrational-resolved electronic spectra of group IV dichlorides using the Franck-Condon approximation combined with the Duschinsky and Herzberg-Teller effects in harmonic and anharmonic frameworks (only the simulation of absorption spectra includes the anharmonicity). Calculated results showed that the band shapes of simulated spectra are in accordance with those of the corresponding experimental or theoretical ones. We found that the symmetric bend mode in progression of absorption is the most active one, whereas the main contributor in photoelectron spectra is the symmetric stretching mode. Moreover, the Duschinsky and anharmonic effects exert weak influence on the absorption spectra, except for PbCl2 molecule. The theoretical insights presented in this work are significant in understanding the photophysical properties of MCl2 (M=C, Si, Ge, Sn, Pb) and studying the Herzberg-Teller and the anharmonic effects on the absorption spectra of new dichlorides of this main group. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. 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.

  15. Dynamics of intramolecular electron transfer reaction of FAD studied by magnetic field effects on transient absorption spectra.

    PubMed

    Murakami, Masaaki; Maeda, Kiminori; Arai, Tatsuo

    2005-07-07

    The kinetics of intermediates generated from intramolecular electron-transfer reaction by photo irradiation of the flavin adenine dinucleotide (FAD) molecule was studied by a magnetic field effect (MFE) on transient absorption (TA) spectra. Existence time of MFE and MFE action spectra have a strong dependence on the pH of solutions. The MFE action spectra have indicated the existence of interconversion between the radical pair and the cation form of the triplet excited state of flavin part. All rate constants of the triplet and the radical pair were determined by analysis of the MFE action spectra and decay kinetics of TA. The obtained values for the interconversion indicate that the formation of cation radical promotes the back electron-transfer reaction to the triplet excited state. Further, rate constants of spin relaxation and recombination have been studied by the time profiles of MFE at various pH. The drastic change of those two factors has been obtained and can be explained by SOC (spin-orbit coupling) induced back electron-transfer promoted by the formation of a stacking conformation at pH > 2.5.

  16. DFT study of electron absorption and emission spectra of pyramidal LnPc(OAc) complexes of some lanthanide ions in the solid state

    NASA Astrophysics Data System (ADS)

    Hanuza, J.; Godlewska, P.; Lisiecki, R.; Ryba-Romanowski, W.; Kadłubański, P.; Lorenc, J.; Łukowiak, A.; Macalik, L.; Gerasymchuk, Yu.; Legendziewicz, J.

    2018-05-01

    The electron absorption and emission spectra were measured for the pyramidal LnPc(OAc) complexes in the solid state and co-doped in silica glass, where Ln = Er, Eu and Ho. The theoretical electron spectra were determined from the quantum chemical DFT calculation using four approximations CAM-B3LYP/LANL2DZ, CAM-B3LYP/CC-PVDZ, B3LYP/LANL2DZ and B3LYP/CC-PVDZ. It was shown that the best agreement between the calculated and experimental structural parameters and spectroscopic data was reached for the CAM-B3LYP/LANL2DZ model. The emission spectra were measured using the excitations both in the ligand and lanthanide absorption ranges. The possibility of energy transfer between the phthalocyanine ligand and excited states of lanthanide ions was discussed. It was shown that the back energy transfer from metal states to phthalocyanine state is responsible for the observed emission of the studied complexes both in the polycrystalline state and silica glass.

  17. Electronic structure of some adenosine receptor antagonists. III. Quantitative investigation of the electronic absorption spectra of alkyl xanthines

    NASA Astrophysics Data System (ADS)

    Moustafa, H.; Shalaby, Samia H.; El-sawy, K. M.; Hilal, Rifaat

    2002-07-01

    Quantitative and comparative investigation of the electronic absorption spectra of theophylline, caffeine and their derivatives is reported. The spectra of theophylline, caffeine and theobromine were compared to establish the predominant tautomeric species in solution. This comparison, analysis of solvent effects and assignments of the observed transitions via MO computations indicate the exits of only one tautomeric species in solution that is the N7 form. A low-lying triplet state was identified which corresponds to a HOMO-LUMO transition. This relatively long-lived T 1 state is always less polar than the ground state and may very well underlie the photochemical reactivity of alkyl xanthines. Substituents of different electron donating or withdrawing strengths and solvent effects are investigated and analyzed. The present analysis is facilitated via computer deconvolution of the observed spectra and MO computation.

  18. A simple approach to spectrally resolved fluorescence and bright field microscopy over select regions of interest

    PubMed Central

    Dahlberg, Peter D.; Boughter, Christopher T.; Faruk, Nabil F.; Hong, Lu; Koh, Young Hoon; Reyer, Matthew A.; Sherani, Aiman; Hammond, Adam T.

    2016-01-01

    A standard wide field inverted microscope was converted to a spatially selective spectrally resolved microscope through the addition of a polarizing beam splitter, a pair of polarizers, an amplitude-mode liquid crystal-spatial light modulator, and a USB spectrometer. The instrument is capable of simultaneously imaging and acquiring spectra over user defined regions of interest. The microscope can also be operated in a bright-field mode to acquire absorption spectra of micron scale objects. The utility of the instrument is demonstrated on three different samples. First, the instrument is used to resolve three differently labeled fluorescent beads in vitro. Second, the instrument is used to recover time dependent bleaching dynamics that have distinct spectral changes in the cyanobacteria, Synechococcus leopoliensis UTEX 625. Lastly, the technique is used to acquire the absorption spectra of CH3NH3PbBr3 perovskites and measure differences between nanocrystal films and micron scale crystals. PMID:27910631

  19. Two-photon-absorption line strengths for nitric oxide: Comparison of theory and sub-Doppler, laser-induced fluorescence measurements

    NASA Astrophysics Data System (ADS)

    Kulatilaka, Waruna D.; Lucht, Robert P.

    2017-03-01

    We discuss the results of high-resolution, sub-Doppler two-photon-absorption laser-induced fluorescence (TPALIF) spectroscopy of nitric oxide at low pressure and room temperature. The measurements were performed using the single-longitudinal mode output of a diode-laser-seeded optical parametric generator (OPG) system with a measured frequency bandwidth of 220 MHz. The measurements were performed using a counter-propagating pump beam geometry, resulting in sub-Doppler TPALIF spectra of NO for various rotational transitions in the (0,0) vibrational band of the A2Σ+ - X2Π electronic transition. The experimental results are compared with the results of a perturbative treatment of the rotational line strengths for the 20 different rotational branches of the X2Π(v″ = 0) → A2Σ+(v' = 0) two-photon absorption band. In the derivation of the expressions for the two-photon transition absorption strength, the closure relation is used for rotational states in the intermediate levels of the two-photon transition in analogy with the Placzek treatment of Raman transitions. The theoretical treatment of the effect of angular momentum coupling on the two-photon rotational line strengths features the use of irreducible spherical tensors and 3j symbols. The final results are expressed in terms of the Hund's case (a) coupling coefficients aJ and bJ for the X2Π(v″ = 0) rotational level wavefunctions, which are intermediate between Hund's case (a) and case (b). Considerable physical insight is provided by this final form of the equations for the rotational line strengths. Corrections to the two-photon absorption rotational line strength for higher order effects such as centrifugal stretching can be included in a straightforward fashion in the analysis by incorporating higher order terms in these coupling coefficients aJ and bJ, although these corrections are essentially negligible for J < 50. The theoretical calculations of relative line intensities are in good agreement both

  20. The absorption- and luminescence spectra of Mn3+ in beryl and vesuvianite

    NASA Astrophysics Data System (ADS)

    Czaja, Maria; Lisiecki, Radosław; Chrobak, Artur; Sitko, Rafał; Mazurak, Zbigniew

    2018-05-01

    The electron absorption-, photoluminescence- and electron paramagnetic-resonance spectra of Mn3+ in red beryl from Wah Wah Mountains (Utah USA) and of pink- and purple vesuvianite from Jeffrey Mine (Asbestos, Canada) were measured at room- and low temperatures. The crystal field stabilization energies are equal to 130.9 kJ/mol for the red beryl, and 151.5-158.0 and 168.0 kJ/mol for for the pink- and the purple vesuvianite, respectively. The red photoluminescence of Mn3+ was not intensive either at room- or at low temperatures. The high Mn content in the crystals caused the emergence of an additional emission band and short photoluminescence-decay lifetimes. The latter are only 183 μs for beryl and 17 μs for vesuvianite.

  1. The absorption- and luminescence spectra of Mn3+ in beryl and vesuvianite

    NASA Astrophysics Data System (ADS)

    Czaja, Maria; Lisiecki, Radosław; Chrobak, Artur; Sitko, Rafał; Mazurak, Zbigniew

    2017-12-01

    The electron absorption-, photoluminescence- and electron paramagnetic-resonance spectra of Mn3+ in red beryl from Wah Wah Mountains (Utah USA) and of pink- and purple vesuvianite from Jeffrey Mine (Asbestos, Canada) were measured at room- and low temperatures. The crystal field stabilization energies are equal to 130.9 kJ/mol for the red beryl, and 151.5-158.0 and 168.0 kJ/mol for for the pink- and the purple vesuvianite, respectively. The red photoluminescence of Mn3+ was not intensive either at room- or at low temperatures. The high Mn content in the crystals caused the emergence of an additional emission band and short photoluminescence-decay lifetimes. The latter are only 183 μs for beryl and 17 μs for vesuvianite.

  2. Intrinsic fluorescence based in-vivo detection of cervical precancer with hand held prototype device

    NASA Astrophysics Data System (ADS)

    Meena, Bharat Lal; Raikwar, Akanksha; Pandey, Kiran; Agarwal, Asha; Pantola, Chayanika; Pradhan, Asima

    2018-02-01

    A prototype device (hand held probe) designed and fabricated in the lab has been tested for cervical precancer detection using intrinsic fluorescence. The intrinsic fluorescence gets strongly modulated by the interplay of scattering and absorption. This masks valuable biochemical information which is present in the intrinsic fluorescence. These distortion effects can be minimized by normalizing the polarized fluorescence spectra by the polarized elastic scattering spectra. The measurements have been made with a in-house fabricated device using a 405 nm diode laser and white light source respectively. 166 sites of different grades of cervical pre-cancer biopsy samples (CIN I and CIN II) (CIN: cervical intraepithelial neoplastic) have been discriminated from 29 sites of normal biopsy samples using principal component analysis (PCA) based linear discriminant analysis (LDA). The sensitivity and specificity for discrimination of normal samples from CIN I are found to be 99% and 96% respectively. Further the normal samples can be discriminated from CIN II samples with 96% sensitivity and 96% specificity. Based on these promising ex-vivo results an in-vivo study on patients has been initiated in the hospital. The hand held device built in-house shows promise as a useful tool for in vivo cervical precancer detection by polarized fluorescence. Preliminary in-vivo results on 10 patients indicate the efficacy of the hand held device for screening cervical precancers using intrinsic fluorescence.

  3. Electronic Absorption and MCD Spectra for Pd(AuPPh(3))(8)(2+), Pt(AuPPh(3))(8)(2+), and Related Platinum-Centered Gold Cluster Complexes.

    PubMed

    Adrowski, Michael J.; Mason, W. Roy

    1997-03-26

    Electronic absorption and 7.0 T magnetic circular dichroism (MCD) spectra in the UV-vis region, 1.6 to approximately 4.0 &mgr;m(-)(1) (1 &mgr;m(-)(1) = 10(4) cm(-)(1)) are reported for [Pd(AuPPh(3))(8)](NO(3))(2) and [Pt(AuPPh(3))(8)](NO(3))(2) in acetonitrile solutions at room temperature. The MCD spectra are better resolved than the absorption spectra and consist of both A and B terms. The spectra are interpreted in terms of D(4)(d)() skeletal geometry and MO's that are approximated by 5s and 6s orbitals for Pd and Pt/Au atoms, respectively. The lowest energy excited configurations and states are attributed to intraframework (IF) Au(8)(2+) transitions. Evidence is also presented for Pt 5d --> Au 6s transitions in the MCD spectra for Pt(AuPPh(3))(8)(2+). Acetonitrile solution absorption and MCD spectra for the related Pt-centered cluster complexes [Pt(CO)(AuPPh(3))(8)](NO(3))(2), [Pt(AuP(p-tolyl)(3))(8)](NO(3))(2), [Pt(CuCl)(AuPPh(3))(8)](NO(3))(2), [Pt(AgNO(3))(AuPPh(3))(8)](NO(3))(2), [Pt(Hg)(2)(AuPPh(3))(8)](NO(3))(2), [Pt(HgCl)(2)(AuPPh(3))(8)](BF(4))(2), and [Pt(HgNO(3))(2)(AuPPh(3))(8)](BF(4))(2) are also reported and interpreted within the context of the model developed for the M(AuPPh(3))(8)(2+) complexes.

  4. 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

    2017-05-17

    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 (Φ PSII ), 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.

  5. X-ray K-edge absorption spectra of Fe minerals and model compounds: II. EXAFS

    NASA Astrophysics Data System (ADS)

    Waychunas, Glenn A.; Brown, Gordon E.; Apted, Michael J.

    1986-01-01

    K-edge extended X-ray absorption fine structure (EXAFS) spectra of Fe in varying environments in a suite of well-characterized silicate and oxide minerals were collected using synchrotron radiation and analyzed using single scattering approximation theory to yield nearest neighbor Fe-O distances and coordination numbers. The partial inverse character of synthetic hercynite spinal was verified in this way. Comparison of the results from all samples with structural data from X-ray diffraction crystal structure refinements indicates that EXAFS-derived first neighbor distances are generally accurate to ±0.02 Å using only theoretically generated phase information, and may be improved over this if similar model compounds are used to determine EXAFS phase functions. Coordination numbers are accurate to ±20 percent and can be similarly improved using model compound EXAFS amplitude information. However, in particular cases the EXAFS-derived distances may be shortened, and the coordination number reduced, by the effects of static and thermal disorder or by partial overlap of the longer Fe-O first neighbor distances with second neighbor distances in the EXAFS structure function. In the former case the total information available in the EXAFS is limited by the disorder, while in the latter case more accurate results can in principle be obtained by multiple neighbor EXAFS analysis. The EXAFS and XANES spectra of Fe in Nain, Labrador osumulite and Lakeview, Oregon plagioclase are also analyzed as an example of the application of X-ray absorption spectroscopy to metal ion site occupation determination in minerals.

  6. Manganese L-edge X-ray absorption spectroscopy of manganese catalase from Lactobacillus plantarum and mixed valence manganese complexes

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Grush, M.M.; Chen, J.; George, S.J.

    1996-01-10

    The first Mn L-edge absorption spectra of a Mn metalloprotein are presented in this paper. Both reduced and superoxidized Mn catalase have been examined by fluorescence-detected soft X-ray absorption spectroscopy, and their Mn L-edge spectra are dramatically different. The spectrum of reduced Mn(II)Mn(II) catalase has been interpreted by ligand field atomic multiplet calculations and by comparison to model compound spectra. The analysis finds a 10 Dq value of nearly 1.1 eV, consistent with coordination by predominately nitrogen and oxygen donor ligands. For interpretation of mixed valence Mn spectra, an empirical simulation procedure based on the addition of homovalent model compoundmore » spectra has been developed and was tested on a variety of Mn complexes and superoxidized Mn catalase. This routine was also used to determine the oxidation state composition of the Mn in [Ba{sub 8}Na{sub 2}ClMn{sub 16}(OH){sub 8}(CO{sub 3}){sub 4}L{sub 8}] .53 H{sub 2}O (L=1,3-diamino-2-hydroxypropane-N,N,N`N`-tetraacetic acid). 27 refs., 6 figs.« less

  7. Quantitative calculations of fluorescence polarization and absorption anisotropy kinetics of double- and triple-chromophore complexes with energy transfer.

    PubMed Central

    Demidov, A A

    1994-01-01

    A new method is presented for calculation of the fluorescence depolarization and kinetics of absorption anisotropy for molecular complexes with a limited number of chromophores. The method considers absorption and emission of light by both chromophores, and also energy transfer between them, with regard to their mutual orientations. The chromophores in each individual complex are rigidly positioned. The complexes are randomly distributed and oriented in space, and there is no energy transfer between them. The new "practical" formula for absorption anisotropy and fluorescence depolarization kinetics, P(t) = [3B(t) - 1 + 2A(t)]/[3 + B(t) + 4A(t)], is derived both for double- and triple-chromophore complexes with delta-pulse excitation. The parameter B(t) is given by (a) B(t) = cos2(theta) for double-chromophore complexes, and (b) B(t) = q12(t)cos2(theta 12) + q13(t)-cos2(theta 13) + q23(t)cos2(theta 23) for triple-chromophore complexes, where q12(t) + q13(t) + q23(t) = 1. Here theta ij are the angles between the chromophore transition dipole moments in the individual molecular complex. The parameters qij(t) and A(t) are dependent on chromophore spectroscopic features and on the rates of energy transfer. PMID:7696461

  8. Direct and Indirect Electron Emission from the Green Fluorescent Protein Chromophore

    NASA Astrophysics Data System (ADS)

    Toker, Y.; Rahbek, D. B.; Klærke, B.; Bochenkova, A. V.; Andersen, L. H.

    2012-09-01

    Photoelectron spectra of the deprotonated green fluorescent protein chromophore have been measured in the gas phase at several wavelengths within and beyond the S0-S1 photoabsorption band of the molecule. The vertical detachment energy (VDE) was determined to be 2.68±0.1eV. The data show that the first electronically excited state is bound in the Franck-Condon region, and that electron emission proceeds through an indirect (resonant) electron-emission channel within the corresponding absorption band.

  9. 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.

  10. A search for formic acid in the upper troposphere - A tentative identification of the 1105-per cm nu-6 band Q branch in high-resolution balloon-borne solar absorption spectra

    NASA Technical Reports Server (NTRS)

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

    1984-01-01

    Infrared solar absorption spectra recorded at 0.02-per cm resolution during a balloon flight from Alamogordo, NM (33 deg N), on March 23, 1981, have been analyzed for the possible presence of absorption by formic acid (HCOOH). An absorption feature at 1105 per cm has been tentatively identified in upper tropospheric spectra as due to the nu-6 band Q branch. A preliminary analysis indicates a concentration of about 0.6 ppbv and 0.4 ppbv near 8 and 10 km, respectively.

  11. 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.

  12. Flow Property Measurement Using Laser-Induced Fluorescence in the NASA Ames Interaction Heating Facility

    NASA Technical Reports Server (NTRS)

    Grinstead, Jay Henderson; Porter, Barry J.; Carballo, Julio Enrique

    2011-01-01

    The spectroscopic diagnostic technique of two photon absorption laser-induced fluorescence (TALIF) of atomic species has been applied to single-point measurements of velocity and static temperature in the NASA Ames Interaction Heating Facility (IHF) arc jet. Excitation spectra of atomic oxygen and nitrogen were recorded while scanning a tunable dye laser over the absorption feature. Thirty excitation spectra were acquired during 8 arc jet runs at two facility operating conditions; the number of scans per run varied between 2 and 6. Curve fits to the spectra were analyzed to recover their Doppler shifts and widths, from which the flow velocities and static temperatures, respectively, were determined. An increase in the number of independent flow property pairs from each as-measured scan was obtained by extracting multiple lower-resolution scans. The larger population sample size enabled the mean property values and their uncertainties for each run to be characterized with greater confidence. The average plus or minus 2 sigma uncertainties in the mean velocities and temperatures for all 8 runs were plus or minus 1.4% and plus or minus 11%, respectively.

  13. Origin of chlorophyll fluorescence in plants at 55-75 degrees C.

    PubMed

    Ilík, Petr; Kouril, Roman; Kruk, Jerzy; Myśliwa-Kurdziel, Beata; Popelková, Hana; Strzałka, Kazimierz; Naus, Jan

    2003-01-01

    The origin of heat-induced chlorophyll fluorescence rise that appears at about 55-60 degrees C during linear heating of leaves, chloroplasts or thylakoids (especially with a reduced content of grana thylakoids) was studied. This fluorescence rise was earlier attributed to photosystem I (PSI) emission. Our data show that the fluorescence rise originates from chlorophyll a (Chl a) molecules released from chlorophyll-containing protein complexes denaturing at 55-60 degrees C. This conclusion results mainly from Chl a fluorescence lifetime measurements with barley leaves of different Chl a content and absorption and emission spectra measurements with barley leaves preheated to selected temperatures. These data, supported by measurements of liposomes with different Chl a/lipid ratios, suggest that the released Chl a is dissolved in lipids of thylakoid membranes and that with increasing Chl a content in the lipid phase, the released Chl a tends to form low-fluorescing aggregates. This is probably the reason for the suppressed fluorescence rise at 55-60 degrees C and the decreasing fluorescence course at 60-75 degrees C, which are observable during linear heating of plant material with a high Chl a/lipid ratio (e.g. green leaves, grana thylakoids, isolated PSII particles).

  14. Single-photon and two-photon excited fluorescence behavior of a novel fluorene-based compound

    NASA Astrophysics Data System (ADS)

    Ma, Wenbo; Wu, Yiquan; Gu, Donghong; Gan, Fuxi

    2005-09-01

    A D-π-D type compound, 2,7-bis(4-methoxystyryl)-9,9-bis(2-ethylhexyl)-9H-fluorene (abbreviated as MO-Flu-MO), where electron-donor D is methoxy group andπis fluorene unit, has been synthesized. The molecular structures of the compound were characterized by elemental analyses, EI-MS and FT-IR spectra. UV-Vis spectra in the region 230--1000 nm and single-photon excited fluorescence in tetrahydrofuran (THF) of the compound were measured. It is found that the new compound exhibits strong two-photon excited fluorescence in the region 380--500 nm and moderate two-photon absorption (TPA) value in the femtoseconds regime (TPA cross-section as high as 55×10-50 cm4 s photon-1 with 13fs laser pulses). The results demonstrate that the compound is a promising candidate for two-photon three-dimensional (3D) optical data storage.

  15. Quantification of zinc-porphyrin in dry-cured ham products by spectroscopic methods Comparison of absorption, fluorescence and X-ray fluorescence spectroscopy.

    PubMed

    Laursen, Kristoffer; Adamsen, Christina E; Laursen, Jens; Olsen, Karsten; Møller, Jens K S

    2008-03-01

    Zinc-protoporphyrin (Zn-pp), which has been identified as the major pigment in certain dry-cured meat products, was extracted with acetone/water (75%) and isolated from the following meat products: Parma ham, Iberian ham and dry-cured ham with added nitrite. The quantification of Zn-pp by electron absorption, fluorescence and X-ray fluorescence (XRF) spectroscopy was compared (concentration range used [Zn-pp]=0.8-9.7μM). All three hams were found to contain Zn-pp, and the results show no significant difference among the content of Zn-pp quantified by fluorescence, absorbance and X-ray fluorescence spectroscopy for Parma ham and Iberian ham. All three methods can be used for quantification of Zn-pp in acetone/water extracts of different ham types if the content is higher than 1.0ppm. For dry-cured ham with added nitrite, XRF was not applicable due to the low content of Zn-pp (<0.1ppm). In addition, XRF spectroscopy provides further information regarding other trace elements and can therefore be advantageous in this aspect. This study also focused on XRF determination of Fe in the extracts and as no detectable Fe was found in the three types of ham extracts investigated (limit of detection; Fe⩽1.8ppm), it allows the conclusion that iron containing pigments, e.g., heme, do not contribute to the noticeable red colour observed in some of the extracts.

  16. Sharp Absorption Peaks in THz Spectra Valuable for Crystal Quality Evaluation of Middle Molecular Weight Pharmaceuticals

    NASA Astrophysics Data System (ADS)

    Sasaki, Tetsuo; Sakamoto, Tomoaki; Otsuka, Makoto

    2018-05-01

    Middle molecular weight (MMW) pharmaceuticals (MW 400 4000) are attracting attention for their possible use in new medications. Sharp absorption peaks were observed in MMW pharmaceuticals at low temperatures by measuring with a high-resolution terahertz (THz) spectrometer. As examples, high-resolution THz spectra for amoxicillin trihydrate, atorvastatin calcium trihydrate, probucol, and α,β,γ,δ-tetrakis(1-methylpyridinium-4-yl)porphyrin p-toluenesulfonate (TMPyP) were obtained at 10 K. Typically observed as peaks with full width at half-height (FWHM) values as low as 5.639 GHz at 0.96492 THz in amoxicillin trihydrate and 8.857 GHz at 1.07974 THz for probucol, many sharp peaks of MMW pharmaceuticals could be observed. Such narrow absorption peaks enable evaluation of the crystal quality of MMW pharmaceuticals and afford sensitive detection of impurities.

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

    NASA Astrophysics Data System (ADS)

    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.

  18. Effect of ladder diagrams on optical absorption spectra in a quasiparticle self-consistent GW framework

    NASA Astrophysics Data System (ADS)

    Cunningham, Brian; Grüning, Myrta; Azarhoosh, Pooya; Pashov, Dimitar; van Schilfgaarde, Mark

    2018-03-01

    We present an approach to calculate the optical absorption spectra that combines the quasiparticle self-consistent GW method [Phys. Rev. B 76, 165106 (2007), 10.1103/PhysRevB.76.165106] for the electronic structure with the solution of the ladder approximation to the Bethe-Salpeter equation for the macroscopic dielectric function. The solution of the Bethe-Salpeter equation has been implemented within an all-electron framework, using a linear muffin-tin orbital basis set, with the contribution from the nonlocal self-energy to the transition dipole moments (in the optical limit) evaluated explicitly. This approach addresses those systems whose electronic structure is poorly described within the standard perturbative GW approaches with density-functional theory calculations as a starting point. The merits of this approach have been exemplified by calculating optical absorption spectra of a strongly correlated transition metal oxide, NiO, and a narrow gap semiconductor, Ge. In both cases, the calculated spectrum is in good agreement with the experiment. It is also shown that for systems whose electronic structure is well-described within the standard perturbative GW , such as Si, LiF, and h -BN , the performance of the present approach is in general comparable to the standard GW plus Bethe-Salpeter equation. It is argued that both vertex corrections to the electronic screening and the electron-phonon interaction are responsible for the observed systematic overestimation of the fundamental band gap and spectrum onset.

  19. The influence of visible light and inorganic pigments on fluorescence excitation emission spectra of egg-, casein- and collagen-based painting media

    NASA Astrophysics Data System (ADS)

    Nevin, A.; Anglos, D.; Cather, S.; Burnstock, A.

    2008-07-01

    Spectrofluorimetric analysis of proteinaceous binding media is particularly promising because proteins employed in paintings are often fluorescent and media from different sources have significantly different fluorescence spectral profiles. Protein-based binding media derived from eggs, milk and animal tissue have been used for painting and for conservation, but their analysis using non-destructive techniques is complicated by interferences with pigments, their degradation and their low concentration. Changes in the fluorescence excitation emission spectra of films of binding media following artificial ageing to an equivalent of 50 and 100 years of museum lighting include the reduction of bands ascribed to tyrosine, tryptophan and Maillard reaction products and an increase in fluorescent photodegradation. Fluorescence of naturally aged paint is dependent on the nature of the pigment present and, with egg-based media, in comparison with un-pigmented films, emissions ascribed to amino acids are more pronounced.

  20. Method for accurate quantitation of background tissue optical properties in the presence of emission from a strong fluorescence marker

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

    Quantification of targeted fluorescence markers during neurosurgery has the potential to improve and standardize surgical distinction between normal and cancerous tissues. However, quantitative analysis of marker fluorescence is complicated by tissue background absorption and scattering properties. Correction algorithms that transform raw fluorescence intensity into quantitative units, independent of absorption and scattering, require a paired measurement of localized white light reflectance to provide estimates of the optical properties. This study focuses on the unique problem of developing a spectral analysis algorithm to extract tissue absorption and scattering properties from white light spectra that contain contributions from both elastically scattered photons and fluorescence emission from a strong fluorophore (i.e. fluorescein). A fiber-optic reflectance device was used to perform measurements in a small set of optical phantoms, constructed with Intralipid (1% lipid), whole blood (1% volume fraction) and fluorescein (0.16-10 μg/mL). Results show that the novel spectral analysis algorithm yields accurate estimates of tissue parameters independent of fluorescein concentration, with relative errors of blood volume fraction, blood oxygenation fraction (BOF), and the reduced scattering coefficient (at 521 nm) of <7%, <1%, and <22%, respectively. These data represent a first step towards quantification of fluorescein in tissue in vivo.

  1. The preparation of ethylenediamine-modified fluorescent carbon dots and their use in imaging of cells.

    PubMed

    Dong, Wei; Zhou, Siqi; Dong, Yan; Wang, Jingwen; Ge, Xin; Sui, Lili

    2015-09-01

    In this work, fluorescent carbon dots (CDs) were synthesized using a hydrothermal method with glucose as the carbon source and were surface-modified with ethylenediamine. The properties of as-prepared CDs were analyzed by transmission electron microscopy (TEM), Fourier transform infrared (FTIR), ultraviolet-visible light (UV/vis) absorption and fluorescent spectra. Furthermore, CDs conjugated with mouse anti-(human carcinoembryonic antigen) (CEA) monoclonal antibody were successful employed in the biolabeling and fluorescent imaging of human gastric carcinoma cells. In addition, the cytotoxicity of CDs was also tested using human gastric carcinoma cells. There was no apparent cytotoxicity on human gastric carcinoma cells. These results suggest the potential application of the as-prepared CDs in bioimaging and related fields. Copyright © 2015 John Wiley & Sons, Ltd.

  2. Laboratory Measurements of Mass Specific Absorption Spectra for Suites of Black Carbon-like, Biomass Burning and Mineral Dust Aerosols

    NASA Astrophysics Data System (ADS)

    Radney, J.; Zangmeister, C.

    2017-12-01

    Light-absorbing atmospheric aerosols can be grouped into three categories: black carbon (BC), brown carbon (BrC) or mineral dust (MD). In many cases, the absorption of these species is best quantified using a mass-specific absorption cross section (MAC) since the particles are in the Rayleigh regime (BC) or optically thin (BrC and MD); notably, MAC values are both traceable to the SI and transferrable between photoacoustic spectroscopy and filter-based absorption measurements. Here, we present laboratory measurements of MAC for all three light-absorbing aerosol classes. Particles were size- and mass-selected using a differential mobility analyzer and aerosol particle mass analyzer, respectively, with absorption coefficients (αabs) and number concentrations (N) being measured by a broadband photoacoustic spectrometer and condensation particle counter, respectively. This suite of instrumentation allows for direct quantification of MAC from the measured parameters (MAC = αabs/Nmp). Further, the measurements contained > 8 data points spanning λ = 405 nm to 840 nm allowing for spectral curvatures (i.e. the Absorption Angstrom Exponent or AAE) to be fit from many data points versus the more common 2-point interpolations. For the carbonaceous, BC-like aerosols - five samples generated from flames, spark discharge soot (i.e. fullerene soot), graphene, reduced graphene oxide (rGO), and fullerene (C60) - we found: 1) measured MAC ranged between 2.4 m2 g-1 and 8.6 m2 g-1 at λ = 550 nm, 2) most AAEs ranged between 0.5 and 1.3; C60 AAE was 7.5 ± 0.9 and 3) MAC spectra were dependent on fuel type and formation conditions. For BrC particles generated from smoldering combustion of 3 hardwood (Oak, Hickory and Mesquite) and 3 softwood species (Western redcedar, Blue spruce and Baldcypress), we found: 1) median MAC values ranged from 1.4 x 10-2 m2 g-1 to 7.9 x 10-2 m2 g-1 at λ = 550 nm, 2) AAE values ranged between 3.5 and 6.2, and 3) Oak, Western redcedar and Blue spruce

  3. DFT study of electron absorption and emission spectra of pyramidal LnPc(OAc) complexes of some lanthanide ions in the solid state.

    PubMed

    Hanuza, J; Godlewska, P; Lisiecki, R; Ryba-Romanowski, W; Kadłubański, P; Lorenc, J; Łukowiak, A; Macalik, L; Gerasymchuk, Yu; Legendziewicz, J

    2018-05-05

    The electron absorption and emission spectra were measured for the pyramidal LnPc(OAc) complexes in the solid state and co-doped in silica glass, where Ln=Er, Eu and Ho. The theoretical electron spectra were determined from the quantum chemical DFT calculation using four approximations CAM-B3LYP/LANL2DZ, CAM-B3LYP/CC-PVDZ, B3LYP/LANL2DZ and B3LYP/CC-PVDZ. It was shown that the best agreement between the calculated and experimental structural parameters and spectroscopic data was reached for the CAM-B3LYP/LANL2DZ model. The emission spectra were measured using the excitations both in the ligand and lanthanide absorption ranges. The possibility of energy transfer between the phthalocyanine ligand and excited states of lanthanide ions was discussed. It was shown that the back energy transfer from metal states to phthalocyanine state is responsible for the observed emission of the studied complexes both in the polycrystalline state and silica glass. Copyright © 2018. Published by Elsevier B.V.

  4. Simulations of fluorescence solvatochromism in substituted PPV oligomers from excited state molecular dynamics with implicit solvent

    DOE PAGES

    Bjorgaard, J. A.; Nelson, T.; Kalinin, K.; ...

    2015-04-28

    In this study, an efficient method of treating solvent effects in excited state molecular dynamics (ESMD) is implemented and tested by exploring the solvatochromic effects in substituted p-phenylene vinylene oligomers. A continuum solvent model is used which has very little computational overhead. This allows simulations of ESMD with solvent effects on the scale of hundreds of picoseconds for systems of up to hundreds of atoms. At these time scales, solvatochromic shifts in fluoresence spectra can be described. Solvatochromic shifts in absorption and fluorescence spectra from ESMD are compared with time-dependent density functional theory calculations and experiments.

  5. [Identification of spill oil species based on low concentration synchronous fluorescence spectra and RBF neural network].

    PubMed

    Liu, Qian-qian; Wang, Chun-yan; Shi, Xiao-feng; Li, Wen-dong; Luan, Xiao-ning; Hou, Shi-lin; Zhang, Jin-liang; Zheng, Rong-er

    2012-04-01

    In this paper, a new method was developed to differentiate the spill oil samples. The synchronous fluorescence spectra in the lower nonlinear concentration range of 10(-2) - 10(-1) g x L(-1) were collected to get training data base. Radial basis function artificial neural network (RBF-ANN) was used to identify the samples sets, along with principal component analysis (PCA) as the feature extraction method. The recognition rate of the closely-related oil source samples is 92%. All the results demonstrated that the proposed method could identify the crude oil samples effectively by just one synchronous spectrum of the spill oil sample. The method was supposed to be very suitable to the real-time spill oil identification, and can also be easily applied to the oil logging and the analysis of other multi-PAHs or multi-fluorescent mixtures.

  6. Visual Understanding of Light Absorption and Waveguiding in Standing Nanowires with 3D Fluorescence Confocal Microscopy

    PubMed Central

    2017-01-01

    Semiconductor nanowires are promising building blocks for next-generation photonics. Indirect proofs of large absorption cross sections have been reported in nanostructures with subwavelength diameters, an effect that is even more prominent in vertically standing nanowires. In this work we provide a three-dimensional map of the light around vertical GaAs nanowires standing on a substrate by using fluorescence confocal microscopy, where the strong long-range disruption of the light path along the nanowire is illustrated. We find that the actual long-distance perturbation is much larger in size than calculated extinction cross sections. While the size of the perturbation remains similar, the intensity of the interaction changes dramatically over the visible spectrum. Numerical simulations allow us to distinguish the effects of scattering and absorption in the nanowire leading to these phenomena. This work provides a visual understanding of light absorption in semiconductor nanowire structures, which is of high interest for solar energy conversion applications. PMID:28966933

  7. Visual Understanding of Light Absorption and Waveguiding in Standing Nanowires with 3D Fluorescence Confocal Microscopy.

    PubMed

    Frederiksen, Rune; Tutuncuoglu, Gozde; Matteini, Federico; Martinez, Karen L; Fontcuberta I Morral, Anna; Alarcon-Llado, Esther

    2017-09-20

    Semiconductor nanowires are promising building blocks for next-generation photonics. Indirect proofs of large absorption cross sections have been reported in nanostructures with subwavelength diameters, an effect that is even more prominent in vertically standing nanowires. In this work we provide a three-dimensional map of the light around vertical GaAs nanowires standing on a substrate by using fluorescence confocal microscopy, where the strong long-range disruption of the light path along the nanowire is illustrated. We find that the actual long-distance perturbation is much larger in size than calculated extinction cross sections. While the size of the perturbation remains similar, the intensity of the interaction changes dramatically over the visible spectrum. Numerical simulations allow us to distinguish the effects of scattering and absorption in the nanowire leading to these phenomena. This work provides a visual understanding of light absorption in semiconductor nanowire structures, which is of high interest for solar energy conversion applications.

  8. Investigation on the pH-dependent binding of benzocaine and lysozyme by fluorescence and absorbance

    NASA Astrophysics Data System (ADS)

    Li, Shihui; Li, Daojin

    2011-11-01

    The interaction mechanism between benzocaine (BZC) and lysozyme (Lys) has been investigated by fluorescence, synchronous fluorescence, ultraviolet-vis (UV) absorption spectra, and three-dimensional fluorescence (3-D) in various pH medium. The observations of fluorescence spectra were mainly rationalized in terms of a static quenching process at lower concentration of BZC ( CBZC/ CLys < 9) and a combined quenching process at higher concentration of BZC ( CBZC/ CLys > 9) at pH 7.4 and 8.4. However, the fluorescence quenching was mainly arisen from static quenching by complex formation in all studied drug concentrations at pH 3.5. The structural characteristics of BZC and Lys were probed, and their binding affinities were determined under different pH conditions (pH 3.5, 7.4, and 8.4). The results indicated that the binding abilities of BZC to Lys decreased at the pH below and above the simulative physiological condition (pH 7.4) due to the alterations of the protein secondary and tertiary structures or the structural change of BZC. The effect of BZC on the conformation of Lys was analyzed using UV, synchronous fluorescence and three-dimensional fluorescence under different pH conditions. These results indicate that the binding of BZC to Lys causes apparent change in the secondary and tertiary structures of Lys. The effect of Zn 2+ on the binding constant of BZC with Lys under various pH conditions (pH 3.5, 7.4, and 8.4) was also studied.

  9. Excitation/Detection Strategies for OH Planar Laser-Induced Fluorescence Measurements in the Presence of Interfering Fuel Signal and Absorption Effects

    NASA Technical Reports Server (NTRS)

    Heath, Christopher M.; Anderson, Robert C.; Hicks, Yolanda R.

    2011-01-01

    Planar laser-induced fluorescence (PLIF) excitation/detection methods have been applied to obtain spatial distributions of the hydroxyl [OH] reacting intermediary and hydrocarbon [HC] primary species in laminar and turbulent combustion reactions. In this report, broadband and narrowband excitation/filtering techniques are explored to identify an optimal experimental configuration yielding significant fluorescent signal with low absorption losses. The combustion environments analyzed include 1) a laminar non-premixed methane/air flame and 2) a turbulent, non-premixed Jet-A/air fueled flame within a lean flame tube combustor. Hydrocarbon-based fuel and OH were excited via the R1 (1), R1(10) and R2(7) transitions of the A(sup 2)Epsilon(+) X(sup 2)pi(1,0) band using a broadband Nd:YAG pumped optical parametric oscillator (OPO) and narrowband Nd:YAG/dye laser with ultraviolet frequency extension (UVX) package. Variables tested for influence on fluorescent signal and absorption characteristics were excitation line, laser energy, exciting linewidth, combustion reactants, and test flow conditions. Results are intended to guide the transition from a dye/UVX laser to an OPO system for performing advanced diagnostics of low-emission combustion concepts.

  10. DFT study of the effect of substituents on the absorption and emission spectra of Indigo

    PubMed Central

    2012-01-01

    Background Theoretical analyses of the indigo dye molecule and its derivatives with Chlorine (Cl), Sulfur (S), Selenium (Se) and Bromine (Br) substituents, as well as an analysis of the Hemi-Indigo molecule, were performed using the Gaussian 03 software package. Results Calculations were performed based on the framework of density functional theory (DFT) with the Becke 3- parameter-Lee-Yang-Parr (B3LYP) functional, where the 6-31 G(d,p) basis set was employed. The configuration interaction singles (CIS) method with the same basis set was employed for the analysis of excited states and for the acquisition of the emission spectra. Conclusions The presented absorption and emission spectra were affected by the substitution position. When a hydrogen atom of the molecule was substituted by Cl or Br, practically no change in the absorbed and emitted energies relative to those of the indigo molecule were observed; however, when N was substituted by S or Se, the absorbed and emitted energies increased. PMID:22809100

  11. FSFE: Fake Spectra Flux Extractor

    NASA Astrophysics Data System (ADS)

    Bird, Simeon

    2017-10-01

    The fake spectra flux extractor generates simulated quasar absorption spectra from a particle or adaptive mesh-based hydrodynamic simulation. It is implemented as a python module. It can produce both hydrogen and metal line spectra, if the simulation includes metals. The cloudy table for metal ionization fractions is included. Unlike earlier spectral generation codes, it produces absorption from each particle close to the sight-line individually, rather than first producing an average density in each spectral pixel, thus substantially preserving more of the small-scale velocity structure of the gas. The code supports both Gadget (ascl:0003.001) and AREPO.

  12. Dual fluorescence of N-phenylanthranilic acid: Effect of solvents, pH and beta-cyclodextrin.

    PubMed

    Rajendiran, N; Balasubramanian, T

    2007-11-01

    Spectral characteristics of N-phenylanthranilic acid (NPAA) have been studied in different solvents, pH and beta-cyclodextrin (beta-CD) and compared with anthranilic acid (2-aminobenzoic acid, 2ABA). In all solvents a dual fluorescence is observed in NPAA, whereas 2ABA gives single emission. Combining the results observed in the absorption, fluorescence emission and fluorescence excitation spectra, it is found that strong intramolecular hydrogen bonding (IHB) interactions present in NPAA molecule. The inclusion complex of NPAA with beta-CD is analysed by UV-vis, fluorimetry, FT-IR, (1)H NMR, scanning electron microscope and AM 1 method. The above spectral studies show that NPAA forms a 1:1 inclusion complex with beta-CD and COOH group present in the beta-CD cavity. A mechanism is proposed to explain the inclusion process.

  13. Dual fluorescence of N-phenylanthranilic acid: Effect of solvents, pH and β-cyclodextrin

    NASA Astrophysics Data System (ADS)

    Rajendiran, N.; Balasubramanian, T.

    2007-11-01

    Spectral characteristics of N-phenylanthranilic acid (NPAA) have been studied in different solvents, pH and β-cyclodextrin (β-CD) and compared with anthranilic acid (2-aminobenzoic acid, 2ABA). In all solvents a dual fluorescence is observed in NPAA, whereas 2ABA gives single emission. Combining the results observed in the absorption, fluorescence emission and fluorescence excitation spectra, it is found that strong intramolecular hydrogen bonding (IHB) interactions present in NPAA molecule. The inclusion complex of NPAA with β-CD is analysed by UV-vis, fluorimetry, FT-IR, 1H NMR, scanning electron microscope and AM 1 method. The above spectral studies show that NPAA forms a 1:1 inclusion complex with β-CD and COOH group present in the β-CD cavity. A mechanism is proposed to explain the inclusion process.

  14. DFT Calculation of IR Absorption Spectra for PCE-nH2O, TCE-nH2O, DCE-nH2O, VC-nH2O for Small and Water-Dominated Molecular Clusters

    DTIC Science & Technology

    2017-10-31

    of isolated molecules and that of bulk systems. DFT calculated absorption spectra represent quantitative estimates that can be correlated with...spectra, can be correlated with the presence of these hydrocarbons (see reference [1]). Accordingly, the molecular structure and IR absorption spectra of...associated with different types of ambient molecules, e.g., H2O, in order to apply background subtraction or spectral-signature- correlation algorithms

  15. Wavelength dispersive analysis with the synchrotron x ray fluorescence microprobe

    NASA Technical Reports Server (NTRS)

    Rivers, M. L.; Thorn, K. S.; Sutton, S. R.; Jones, K. W.; Bajt, S.

    1993-01-01

    A wavelength dispersive spectrometer (WDS) was tested on the synchrotron x ray fluorescence microprobe at Brookhaven National Laboratory. Compared to WDS spectra using an electron microprobe, the synchrotron WDS spectra have much better sensitivity and, due to the absence of bremsstrahlung radiation, lower backgrounds. The WDS spectrometer was successfully used to resolve REE L fluorescence spectra from standard glasses and transition metal K fluorescence spectra from kamacite.

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  17. Laser-Induced Fluorescence (LIF) from plant foliage

    NASA Technical Reports Server (NTRS)

    Chappelle, E. W.; Williams, D. L.

    1986-01-01

    The fluorescence spectra and fluorescence induction kinetics of green plants excited at 337 nm by a laser were studied. They correlate with plant type, as well as with changes in the physiology of the plant as the result of stress. The plant types studied include herbaceous dicots, monocots, hardwoods, conifers, and algae. These plant types could be identified on the basis of differences in either the number of fluorescent bands or the relative intensity of the bands. Differences in fluorescent spectra which could be related to vigor status are observed in conifers located in an area of high atmospheric deposition. Changes in the fluorescence spectra and induction kinetics are also seen in plants grown under conditions of nutrient deficiency and drought stress.

  18. Laser-Induced Fluorescence (LIF) from plant foliage

    NASA Technical Reports Server (NTRS)

    Chappelle, Emmett W.; Williams, Darrel L.

    1987-01-01

    The fluorescence spectra and fluorescence induction kinetics of green plants excited at 337 nm by a laser were studied. They correlate with plant type, as well as with changes in the physiology of the plant as the result of stress. The plant types studied include herbaceous dicots, monocots, hardwoods, conifers, and algae. These plant types could be identified on the basis of differences in either the number of fluorescent bands or the relative intensity of the bands. Differences in fluorescent spectra which could be related to vigor status are observed in conifers located in an area of high atmospheric deposition. Changes in the fluorescence spectra and induction kinetics are also seen in plants grown under conditions of nutrient deficiency and drought stress.

  19. Optical filters for wavelength selection in fluorescence instrumentation.

    PubMed

    Erdogan, Turan

    2011-04-01

    Fluorescence imaging and analysis techniques have become ubiquitous in life science research, and they are poised to play an equally vital role in in vitro diagnostics (IVD) in the future. Optical filters are crucial for nearly all fluorescence microscopes and instruments, not only to provide the obvious function of spectral control, but also to ensure the highest possible detection sensitivity and imaging resolution. Filters make it possible for the sample to "see" light within only the absorption band, and the detector to "see" light within only the emission band. Without filters, the detector would not be able to distinguish the desired fluorescence from scattered excitation light and autofluorescence from the sample, substrate, and other optics in the system. Today the vast majority of fluorescence instruments, including the widely popular fluorescence microscope, use thin-film interference filters to control the spectra of the excitation and emission light. Hence, this unit emphasizes thin-film filters. After briefly introducing different types of thin-film filters and how they are made, the unit describes in detail different optical filter configurations in fluorescence instruments, including both single-color and multicolor imaging systems. Several key properties of thin-film filters, which can significantly affect optical system performance, are then described. In the final section, tunable optical filters are also addressed in a relative comparison.

  20. 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.

  1. Two photon absorption laser induced fluorescence measurements of neutral density in a helicon plasma

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    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 deuteriummore » 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.« less

  2. Vibrational, X-ray absorption, and Mössbauer spectra of sulfate minerals from the weathered massive sulfide deposit at Iron Mountain, California

    USGS Publications Warehouse

    Majzlan, Juraj; Alpers, Charles N.; Bender Koch, Christian; McCleskey, R. Blaine; Myneni, Satish B.C.; Neil, John M.

    2011-01-01

    The Iron Mountain Mine Superfund site in California is a prime example of an acid mine drainage (AMD) system with well developed assemblages of sulfate minerals typical for such settings. Here we present and discuss the vibrational (infrared), X-ray absorption, and M??ssbauer spectra of a number of these phases, augmented by spectra of a few synthetic sulfates related to the AMD phases. The minerals and related phases studied in this work are (in order of increasing Fe2O3/FeO): szomolnokite, rozenite, siderotil, halotrichite, r??merite, voltaite, copiapite, monoclinic Fe2(SO4)3, Fe2(SO4)3??5H2O, kornelite, coquimbite, Fe(SO4)(OH), jarosite and rhomboclase. Fourier transform infrared spectra in the region 750-4000cm-1 are presented for all studied phases. Position of the FTIR bands is discussed in terms of the vibrations of sulfate ions, hydroxyl groups, and water molecules. Sulfur K-edge X-ray absorption near-edge structure (XANES) spectra were collected for selected samples. The feature of greatest interest is a series of weak pre-edge peaks whose position is determined by the number of bridging oxygen atoms between Fe3+ octahedra and sulfate tetrahedra. M??ssbauer spectra of selected samples were obtained at room temperature and 80K for ferric minerals jarosite and rhomboclase and mixed ferric-ferrous minerals r??merite, voltaite, and copiapite. Values of Fe2+/[Fe2++Fe3+] determined by M??ssbauer spectroscopy agree well with those determined by wet chemical analysis. The data presented here can be used as standards in spectroscopic work where spectra of well-characterized compounds are required to identify complex mixtures of minerals and related phases. ?? 2011 Elsevier B.V.

  3. Vibrational, X-ray absorption, and Mössbauer spectra of sulfate minerals from the weathered massive sulfide deposit at Iron Mountain, California

    USGS Publications Warehouse

    Majzlan, Juraj; Alpers, Charles N.; Bender Koch, Christian; McCleskey, R. Blaine; Myneni, Satish B.C.; Neil, John M.

    2014-01-01

    The Iron Mountain Mine Superfund site in California is a prime example of an acid mine drainage (AMD) system with well developed assemblages of sulfate minerals typical for such settings. Here we present and discuss the vibrational (infrared), X-ray absorption, and Mössbauer spectra of a number of these phases, augmented by spectra of a few synthetic sulfates related to the AMD phases. The minerals and related phases studied in this work are (in order of increasing Fe2O3/FeO): szomolnokite, rozenite, siderotil, halotrichite, römerite, voltaite, copiapite, monoclinic Fe2(SO4)3, Fe2(SO4)3·5H2O, kornelite, coquimbite, Fe(SO4)(OH), jarosite and rhomboclase. Fourier transform infrared spectra in the region 750–4000 cm−1 are presented for all studied phases. Position of the FTIR bands is discussed in terms of the vibrations of sulfate ions, hydroxyl groups, and water molecules. Sulfur K-edge X-ray absorption near-edge structure (XANES) spectra were collected for selected samples. The feature of greatest interest is a series of weak pre-edge peaks whose position is determined by the number of bridging oxygen atoms between Fe3+ octahedra and sulfate tetrahedra. Mössbauer spectra of selected samples were obtained at room temperature and 80 K for ferric minerals jarosite and rhomboclase and mixed ferric–ferrous minerals römerite, voltaite, and copiapite. Values of Fe2+/[Fe2+ + Fe3+] determined by Mössbauer spectroscopy agree well with those determined by wet chemical analysis. The data presented here can be used as standards in spectroscopic work where spectra of well-characterized compounds are required to identify complex mixtures of minerals and related phases.

  4. Compact point-detection fluorescence spectroscopy system for quantifying intrinsic fluorescence redox ratio in brain cancer diagnostics

    NASA Astrophysics Data System (ADS)

    Liu, Quan; Grant, Gerald; Li, Jianjun; Zhang, Yan; Hu, Fangyao; Li, Shuqin; Wilson, Christy; Chen, Kui; Bigner, Darell; Vo-Dinh, Tuan

    2011-03-01

    We report the development of a compact point-detection fluorescence spectroscopy system and two data analysis methods to quantify the intrinsic fluorescence redox ratio and diagnose brain cancer in an orthotopic brain tumor rat model. Our system employs one compact cw diode laser (407 nm) to excite two primary endogenous fluorophores, reduced nicotinamide adenine dinucleotide, and flavin adenine dinucleotide. The spectra were first analyzed using a spectral filtering modulation method developed previously to derive the intrinsic fluorescence redox ratio, which has the advantages of insensitivty to optical coupling and rapid data acquisition and analysis. This method represents a convenient and rapid alternative for achieving intrinsic fluorescence-based redox measurements as compared to those complicated model-based methods. It is worth noting that the method can also extract total hemoglobin concentration at the same time but only if the emission path length of fluorescence light, which depends on the illumination and collection geometry of the optical probe, is long enough so that the effect of absorption on fluorescence intensity due to hemoglobin is significant. Then a multivariate method was used to statistically classify normal tissues and tumors. Although the first method offers quantitative tissue metabolism information, the second method provides high overall classification accuracy. The two methods provide complementary capabilities for understanding cancer development and noninvasively diagnosing brain cancer. The results of our study suggest that this portable system can be potentially used to demarcate the elusive boundary between a brain tumor and the surrounding normal tissue during surgical resection.

  5. Near-infrared fluorescence amplified organic nanoparticles with aggregation-induced emission characteristics for in vivo imaging

    NASA Astrophysics Data System (ADS)

    Geng, Junlong; Zhu, Zhenshu; Qin, Wei; Ma, Lin; Hu, Yong; Gurzadyan, Gagik G.; Tang, Ben Zhong; Liu, Bin

    2013-12-01

    Near-infrared (NIR) fluorescence signals are highly desirable to achieve high resolution in biological imaging. To obtain NIR emission with high brightness, fluorescent nanoparticles (NPs) are synthesized by co-encapsulation of 2,3-bis(4-(phenyl(4-(1,2,2-triphenylvinyl)phenylamino)phenyl)fumaronitrile (TPETPAFN), a luminogen with aggregation-induced emission (AIE) characteristics, and a NIR fluorogen of silicon 2,3-naphthalocyanine bis(trihexylsilyloxide) (NIR775) using 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethylene glycol)-2000] as the encapsulation matrix. The good spectral overlap between the emission of TPETPAFN and the absorption of NIR775 leads to efficient energy transfer, resulting in a 47-fold enhancement of the NIR775 emission intensity upon excitation of TPETPAFN at 510 nm as compared to that upon direct excitation of NIR775 at 760 nm. The obtained fluorescent NPs show sharp NIR emission with a band width of 20 nm, a large Stokes shift of 275 nm, good photostability and low cytotoxicity. In vivo imaging study reveals that the synthesized NPs are able to provide high fluorescence contrast in live animals. The Förster resonance energy transfer strategy overcomes the intrinsic limitation of broad emission spectra for AIE NPs, which opens new opportunities to synthesize organic NPs with high brightness and narrow emission for potential applications in multiplex sensing and imaging.Near-infrared (NIR) fluorescence signals are highly desirable to achieve high resolution in biological imaging. To obtain NIR emission with high brightness, fluorescent nanoparticles (NPs) are synthesized by co-encapsulation of 2,3-bis(4-(phenyl(4-(1,2,2-triphenylvinyl)phenylamino)phenyl)fumaronitrile (TPETPAFN), a luminogen with aggregation-induced emission (AIE) characteristics, and a NIR fluorogen of silicon 2,3-naphthalocyanine bis(trihexylsilyloxide) (NIR775) using 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethylene glycol)-2000

  6. 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.

  7. Two-photon absorption laser-induced fluorescence measurements of atomic nitrogen in a radio-frequency atmospheric-pressure plasma jet

    NASA Astrophysics Data System (ADS)

    Wagenaars, E.; Gans, T.; O'Connell, D.; Niemi, K.

    2012-08-01

    The first direct measurements of atomic nitrogen species in a radio-frequency atmospheric-pressure plasma jet (APPJ) are presented. Atomic nitrogen radicals play a key role in new plasma medicine applications of APPJs. The measurements were performed with a two-photon absorption laser-induced fluorescence diagnostic, using 206.65 nm laser photons for the excitation of ground-state N atoms and observing fluorescence light around 744 nm. The APPJ was run with a helium gas flow of 1 slm and varying small admixtures of molecular nitrogen of 0-0.7 vol%. A maximum in the measured N concentration was observed for an admixture of 0.25 vol% N2.

  8. FRET Studies Between CdTe Capped by Small-Molecule Ligands and Fluorescent Protein

    NASA Astrophysics Data System (ADS)

    Zhang, Yue; Zhou, Dejian; He, Junhui

    2014-12-01

    Water-soluble luminescent semiconductor nanocrystals also known as quantum dots (QDs) that have prominent photostability, wide absorption cross sections and tunable narrow emission, have been shown as promising probes in immunoassays. QDs are often used as donors in fluorescence resonance energy transfer (FRET) based sensors using organic dyes or fluorescent proteins as acceptors. Here, the FRET between a QD donor and fluorescent protein acceptors has been studied. The fluorescent protein (FP)mCherry appended with a hexa-histidine-tag could effectively self-assemble onto CdTe to produce small donor-acceptor distances and hence highly efficient FRET (efficiency > 80%) at relatively low FP:CdTe copy numbers (ca.1). Using the Förster dipole-dipole interaction formula, the Förster radius (R0) and respective donor-acceptor distances for the CdTe-FP FRET systems have been calculated. The binding constants (Kd) of the QD-FP systems have also been evaluated by the emission spectra.

  9. Spectroscopic characterization of C7H3(+) and C7H3˙: electronic absorption and fluorescence in 6 K neon matrices.

    PubMed

    Chakraborty, Arghya; Fulara, Jan; Dietsche, Rainer; Maier, John P

    2014-04-21

    Mass selective deposition of C7H3(+) (m/z = 87) into solid neon reveals the 1(1)A1←X(1)A1 electronic absorption system of hepta-1,2,3,4,5,6-heptahexaenylium cation B(+) [H2CCCCCCCH](+) with an origin band at 441.3 nm, 1(1)A'←X(1)A' transition of 2,4-pentadiynylium,1-ethynyl cation C(+) [HCCCHCCCCH](+) starting at 414.6 nm and the 1(1)A1←X(1)A1 one of cyclopropenylium,1,3-butadiynyl cation A(+) [HCCCCC<(CH=CH)](+) with an onset at 322.2 nm. Vibrationally resolved fluorescence was observed for isomer B(+) upon laser excitation of the absorption bands in the 1(1)A1←X(1)A1 transition. After neutralization of the cations in the matrix five absorption systems of the C7H3 neutral radicals starting at 530.3, 479.4, 482.3, 325.0 and 302.5 nm were detected. These were identified as the 1(2)A'←X(2)A' and 2(2)A'←X(2)A' electronic transitions of 2-(buta-1,3-diynyl)cycloprop-2yl-1-1ylidene E˙ [HCCCCC<(C=CH2)]˙, 1(2)B1←X(2)B1 of 1,2,3,4,5,6-heptahexaenyl B˙ [H2CCCCCCCH]˙, 3(2)B1←X(2)B1 of 3-buta-1,3-diynyl-cyclopropenyl A˙ [HCCCCC<(CH=CH)]˙ and 2(2)B1←X(2)A2 transition of 1,2-divinylidene-cyclopropanyl radical F˙ [HCC-cyc-(CCHC)-CCH]˙, respectively. The assignment is based on calculated vertical excitation energies using the CASPT2 method. Comparison of the calculated harmonic vibrational frequencies with those inferred from the spectra supports the assignment.

  10. Application of normal fluorescence and stability-indicating derivative synchronous fluorescence spectroscopy for the determination of gliquidone in presence of its fluorescent alkaline degradation product

    NASA Astrophysics Data System (ADS)

    El-ghobashy, Mohamed R.; Yehia, Ali M.; Helmy, Aya H.; Youssef, Nadia F.

    2018-01-01

    Simple, smart and sensitive normal fluorescence and stability-indicating derivative synchronous spectrofluorimetric methods have been developed and validated for the determination of gliquidone in the drug substance and drug product. Normal spectrofluorimetric method of gliquidone was established in methanol at λ excitation 225 nm and λ emission 400 nm in concentration range 0.2-3 μg/ml with LOD equal 0.028. The fluorescence quantum yield of gliquidone was calculated using quinine sulfate as a reference and found to be 0.542. Stability-indicating first and third derivative synchronous fluorescence spectroscopy were successfully utilized to overcome the overlapped spectra in normal fluorescence of gliquidone and its alkaline degradation product. Derivative synchronous methods are based on using the synchronous fluorescence of gliquidone and its degradation product in methanol at Δ λ50 nm. Peak amplitude in the first derivative of synchronous fluorescence spectra was measured at 309 nm where degradation product showed zero-crossing without interference. The peak amplitudes in the third derivative of synchronous fluorescence spectra, peak to trough were measured at 316,329 nm where degradation product showed zero-crossing. The different experimental parameters affecting the normal and synchronous fluorescence intensity of gliquidone were studied and optimized. Moreover, the cited methods have been validated as per ICH guidelines. The peak amplitude-concentration plots of the derivative synchronous fluorescence were linear over the concentration range 0.05-2 μg/ml for gliquidone. Limits of detection were 0.020 and 0.022 in first and third derivative synchronous spectra, respectively. The adopted methods were successfully applied to commercial tablets and the results demonstrated that the derivative synchronous fluorescence spectroscopy is a powerful stability-indicating method, suitable for routine use with a short analysis time. Statistical comparison between

  11. Fluorescence and Nonlinear Optical Properties of Alizarin Red S in Solvents and Droplet.

    PubMed

    Sangsefedi, Seyed Ahmad; Sharifi, Soheil; Rezaion, Hadi Rastegar Moghaddam; Azarpour, Afshin

    2018-05-28

    The enhancement of the nonlinear properties of materials is an interesting topic since it has many applications in optical devices and medicines. The Z-scan technique was used to study the values of the two-photon absorption (β), second-order molecular hyperpolarizability (γ R ), third-order susceptibility (χ R ), and nonlinear refractive index (n 2 ) of Alizarin Red S in different media using a continuous-wave diode-pump laser radiation at 532 nm. For Alizarin Red S in a droplet, the β, n 2 , χ R, and γ R were estimated at the order of 10 -7  cm 2 /W and 10 -12  cm/W, 10 -3  m 3  W -1  s -1 and 10 -24  m 6  W -1  s -1 , respectively. The results indicated that the values of β and n 2 reduced, whereas the values of χ R and γ R were enhanced when the solvent was changed from droplet to water, DMF, and dimethyl sulfoxide due to the change in the solvent's dielectric constant (ε). Moreover, the values of β were enhanced by an increase in the concentration of the surfactant in the aqueous solution. The absorption spectra of Alizarin Red S in the aqueous solution was observed at 428 nm, and a few red shifts in the absorption spectra were observed with a reduction in the dielectric constant of the medium. The same effect was observed in the absorption spectra of Alizarin Red S in the droplet when the bulk dielectric constant reduced. The dielectric constant can affect the fluorescence spectra of Alizarin Red S when the solution is changed from water to dimethyl sulfoxide. The dipole moments of Alizarin Red S in the different media were studied using the quantum perturbation theory.

  12. Temperature dependence of metal-enhanced fluorescence of photosystem I from Thermosynechococcus elongatus.

    PubMed

    Ashraf, Imran; Konrad, Alexander; Lokstein, Heiko; Skandary, Sepideh; Metzger, Michael; Djouda, Joseph M; Maurer, Thomas; Adam, Pierre M; Meixner, Alfred J; Brecht, Marc

    2017-03-23

    We report the temperature dependence of metal-enhanced fluorescence (MEF) of individual photosystem I (PSI) complexes from Thermosynechococcus elongatus (T. elongatus) coupled to gold nanoparticles (AuNPs). A strong temperature dependence of shape and intensity of the emission spectra is observed when PSI is coupled to AuNPs. For each temperature, the enhancement factor (EF) is calculated by comparing the intensity of individual AuNP-coupled PSI to the mean intensity of 'uncoupled' PSI. At cryogenic temperature (1.6 K) the average EF was 4.3-fold. Upon increasing the temperature to 250 K the EF increases to 84-fold. Single complexes show even higher EFs up to 441.0-fold. At increasing temperatures the different spectral pools of PSI from T. elongatus become distinguishable. These pools are affected differently by the plasmonic interactions and show different enhancements. The remarkable increase of the EFs is explained by a rate model including the temperature dependence of the fluorescence yield of PSI and the spectral overlap between absorption and emission spectra of AuNPs and PSI, respectively.

  13. Intrinsic photosensitizer fluorescence measured using multi-diameter single-fiber spectroscopy in vivo

    NASA Astrophysics Data System (ADS)

    van Leeuwen-van Zaane, Floor; Gamm, Ute A.; van Driel, Pieter B. A. A.; Snoeks, Thomas J.; de Bruijn, Henriette S.; van der Ploeg-van den Heuvel, Angelique; Sterenborg, Henricus J. C. M.; Löwik, Clemens W.; Amelink, Arjen; Robinson, Dominic J.

    2014-01-01

    Quantification of fluorescence in vivo is complicated by the influence of tissue optical properties on the collected fluorescence signal. When tissue optical properties in the measurement volume are quantified, one can obtain the intrinsic fluorescence, which equals the product of fluorophore absorption coefficient and quantum yield. We applied this method to in vivo single-fiber fluorescence spectroscopy measurements on mouse tongue, skin, liver, and oral squamous cell carcinoma, where we detected intrinsic fluorescence spectra of the photosensitizers chlorin e6 and Bremachlorin at t=[3,4.5,6,24,48] h incubation time. We observed a tissue-dependent maximum of 35% variation in the total correction factor over the visible wavelength range. Significant differences in spectral shape over time between sensitizers were observed. Although the wavelength position of the fluorescence intensity maximum for ce6 shifted to the red, Bremachlorin showed a blue shift. Furthermore, the Bremachlorin peak appeared to be broader than the ce6 fluorescence peak. Intrinsic fluorescence intensity, which can be related to photosensitizer concentration, was decreasing for all time points but showed significantly more Bremachlorin present compared to ce6 at long incubation times. Results from this study can be used to define an optimal treatment protocol for Bremachlorin-based photodynamic therapy.

  14. A highly selective colorimetric and fluorescent chemosensor for Al(III) based-on simple naphthol in aqueous solution

    NASA Astrophysics Data System (ADS)

    Liu, Zhaodi; Xu, Huajie; Sheng, Liangquan; Chen, Shuisheng; Huang, Deqian; Liu, Jie

    2016-03-01

    A colorimetric and fluorescent chemosensor (L) for Al(III) was synthesized and fully characterized. L could be both used as a colorimetric and fluorescent chemosensor for the detection of Al3 + ions with low detection limit (8.87 × 10- 7 M) in CH3CN-H2O (1:1, v/v) solution. The binding ratio of L-Al3 + was determined from the Job plot (absorption and fluorescence spectra) and MALDI-TOF MS data to be 1:1. The binding constant (Ka) of Al3 + binding to L was calculated to be 4.8 × 105 M- 1 from a Benesi-Hildebrand plot. Moreover, the binding site of L with Al3 + was determined by 1H NMR titration experiment.

  15. Facile preparation of fluorescent layered double hydroxide polymeric composites through the photo-induced surface-initiated controlled living polymerization

    NASA Astrophysics Data System (ADS)

    Chen, Junyu; Liu, Meiying; Huang, Qiang; Jiang, Ruming; Huang, Hongye; Deng, Fengjie; Wen, Yuanqing; Tian, Jianwen; Zhang, Xiaoyong; Wei, Yen

    2018-05-01

    (Zn/Al) layered double hydroxide (LDH) based fluorescence probes have been facilely fabricated via photo-induced surface-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization, which demonstrated green fluorescence, good biocompatibility and excellent dispersion performance in aqueous solution. The as prepared (Zn/Al)LDH polymeric composites were modified with 2-methacryloyloxyethyl phosphorylcholine (MPC), acrylic acid (AA) and diacroloyl-fluorescein (Ac-Fl). Among them, the comonomers MPC and AA were used to endow their water dispersibility, biocompatibility and potential drug carriers, while the Ac-Fl was served both as the fluorescence signal and photocatalyst for RAFT polymerization. A series of characterization methods, including 1H nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, transmission electronic microscopy, thermogravimetric analyses, X-ray photoelectron spectroscopy were employed to conform the successful of surface modification of LDH through photo-induced surface-initiated RAFT polymerization. Besides, UV-vis absorption spectra and fluorescence spectra were adopted to evaluate the optical characteristics of as prepared (Zn/Al)LDH-co-Poly(MPC-AA-Fl) composites, which exhibited high intense green fluorescence. Furthermore, the endocytosis behavior indicates that (Zn/Al)LDH-co-Poly(MPC-AA-Fl) composites could be potentially used in cell imaging and even drug delivery application for their excellent biocompatibility and all advantages described above.

  16. Hydrological and Biogeochemical Controls on Absorption and Fluorescence of Dissolved Organic Matter in the Northern South China Sea

    NASA Astrophysics Data System (ADS)

    Wang, Chao; Guo, Weidong; Li, Yan; Stubbins, Aron; Li, Yizhen; Song, Guodong; Wang, Lei; Cheng, Yuanyue

    2017-12-01

    The Kuroshio intrusion from the West Philippine Sea (WPS) and mesoscale eddies are important hydrological features in the northern South China Sea (SCS). In this study, absorption and fluorescence of dissolved organic matter (CDOM and FDOM) were determined to assess the impact of these hydrological features on DOM dynamics in the SCS. DOM in the upper 100 m of the northern SCS had higher absorption, fluorescence, and degree of humification than in the Kuroshio Current of the WPS. The results of an isopycnal mixing model showed that CDOM and humic-like FDOM inventories in the upper 100 m of the SCS were modulated by the Kuroshio intrusion. However, protein-like FDOM was influenced by in situ processes. This basic trend was modified by mesoscale eddies, three of which were encountered during the fieldwork (one warm eddy and two cold eddies). DOM optical properties inside the warm eddy resembled those of DOM in the WPS, indicating that warm eddies could derive from the Kuroshio Current through Luzon Strait. DOM at the center of cold eddies was enriched in humic-like fluorescence and had lower spectral slopes than in eddy-free waters, suggesting inputs of humic-rich DOM from upwelling and enhanced productivity inside the eddy. Excess CDOM and FDOM in northern SCS intermediate water led to export to the Pacific Ocean interior, potentially delivering refractory carbon to the deep ocean. This study demonstrated that DOM optical properties are promising tools to study active marginal sea-open ocean interactions.

  17. Two-photon absorption properties of cationic 1,4-bis(styryl)benzene derivative and its inclusion complexes with cyclodextrins.

    PubMed

    Nag, Okhil Kumar; Nayak, Rati Ranjan; Lim, Chang Su; Kim, In Hong; Kyhm, Kwangseuk; Cho, Bong Rae; Woo, Han Young

    2010-07-29

    Two-photon absorption properties of 1,4-bis{4'-[N,N-bis(6''-trimethylammoniumhexyl)amino]styryl}benzene tetrabromide (C1) and its inclusion complexes (ICs) with cyclodextrins (CDs) have been studied. Upon complexation with CDs, the absorption spectra of C1 showed a slight red shift, whereas the emission spectra showed a blue shift with concomitant increase in the fluorescence quantum efficiency. A Stern-Volmer study using K(3)Fe(CN)(6) as a quencher revealed significant reduction in the photoinduced charge transfer quenching, in accord with the IC formation. Comparison of the spectroscopic results reveals that C1 forms increasingly more stable ICs in the order C1/beta-CD < C1/gamma-CD < C1/(3gamma:beta)-CD (gamma-CD/beta-CD 3:1, mole ratio). Moreover, the two-photon action cross section of C1 increased from 200 GM for C1 to 400 GM for C1/beta-CD, 460 GM for C1/gamma-CD, and 650 GM for C1/(3gamma:beta)-CD, respectively. Furthermore, the two-photon microscopy images of HeLa cells stained with C1 emitted strong two-photon excited fluorescence in the plasma membrane. These results provide a useful guideline for the development of efficient two-photon materials for bioimaging applications.

  18. Absorption spectra and optical transitions in InAs/GaAs self-assembled quantum dots

    NASA Astrophysics Data System (ADS)

    Cusack, M. A.; Briddon, P. R.; Jaros, M.

    1997-08-01

    We have applied the multiband effective mass/valence force field method to the calculation of optical transitions and absorption spectra in InAs/GaAs self-organized dots of different sizes. We have found that the apparently conflicting assignments of luminescence features to optical transitions in different experiments are in fact entirely compatible with each other. Whether the optical signature of a dot is constructed from transitions between states of the same quantum numbers, or via additional processes between the ground conduction state and a low-lying valence state depends on the aspect ratio of the quantum dot radius and height. The states involved can be predicted from a simple particle in a rigid rectangular box model.

  19. Signatures of a conical intersection in photofragment distributions and absorption spectra: Photodissociation in the Hartley band of ozone

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Picconi, David; Grebenshchikov, Sergy Yu., E-mail: Sergy.Grebenshchikov@ch.tum.de

    Photodissociation of ozone in the near UV is studied quantum mechanically in two excited electronic states coupled at a conical intersection located outside the Franck-Condon zone. The calculations, performed using recent ab initio PESs, provide an accurate description of the photodissociation dynamics across the Hartley/Huggins absorption bands. The observed photofragment distributions are reproduced in the two electronic dissociation channels. The room temperature absorption spectrum, constructed as a Boltzmann average of many absorption spectra of rotationally excited parent ozone, agrees with experiment in terms of widths and intensities of diffuse structures. The exit channel conical intersection contributes to the coherent broadeningmore » of the absorption spectrum and directly affects the product vibrational and translational distributions. The photon energy dependences of these distributions are strikingly different for fragments created along the adiabatic and the diabatic paths through the intersection. They can be used to reverse engineer the most probable geometry of the non-adiabatic transition. The angular distributions, quantified in terms of the anisotropy parameter β, are substantially different in the two channels due to a strong anticorrelation between β and the rotational angular momentum of the fragment O{sub 2}.« less

  20. Composite fluorescent nanoparticles for biomedical imaging.

    PubMed

    Pansare, Vikram J; Bruzek, Matthew J; Adamson, Douglas H; Anthony, John; Prud'homme, Robert K

    2014-04-01

    In the rapidly expanding field of biomedical imaging, there is a need for nontoxic, photostable, and nonquenching fluorophores for fluorescent imaging. We have successfully encapsulated a new, extremely hydrophobic, pentacene-based fluorescent dye within polymeric nanoparticles (NPs) or nanocarriers (NCs) via the Flash NanoPrecipitation (FNP) process. Nanoparticles and dye-loaded micelles were formulated by FNP and characterized by dynamic light scattering, fluorescence spectroscopy, UV-VIS absorbance spectroscopy, and confocal microscopy. These fluorescent particles were loaded from less than 1% to 78% by weight core loading and the fluorescence maximum was found to be at 2.3 wt.%. The particles were also stably formed at 2.3% core loading from 20 up to 250 nm in diameter with per-particle fluorescence scaling linearly with the NC core volume. The major absorption peaks are at 458, 575, and 625 nm, and the major emission peaks at 635 and 695 nm. In solution, the Et-TP5 dye displays a strong concentration-dependent ratio of the emission intensities of the first two emission peaks, whereas in the nanoparticle core the spectrum is independent of concentration over the entire concentration range. A model of the fluorescence quenching was consistent with Förster resonant energy transfer as the cause of the quenching observed for Et-TP5. The Förster radius calculated from the absorption and emission spectra of Et-TP5 is 4.1 nm, whereas the average dye spacing in the particles at the maximum fluorescence is 3.9 nm. We have successfully encapsulated Et-TP5, a pentacene derivative dye previously only used in light-emitting diode applications, within NCs via the FNP process. The extreme hydrophobicity of the dye keeps it encapsulated in the NC core, its extended pentacene structure gives it relatively long wavelength emission at 695 nm, and the pentacene structure, without oxygen or nitrogen atoms in its core, makes it highly resistant to photobleaching. Its bulky side

  1. In-Vivo Fluorescence Spectroscopy Of Normal And Atherosclerotic Arteries

    NASA Astrophysics Data System (ADS)

    Deckelbaum, Lawrence I.; Sarembock, Ian J.; Stetz, Mark L.; O'Brien, Kenneth M.; Cutruzzola, Francis W.; Gmitro, Arthur F.; Ezekowitz, Michael D.

    1988-06-01

    Laser-induced fluorescence spectroscopy can discriminate atherosclerotic from normal arteries in-vitro and may thus potentially guide laser angioplasty. To evaluate the feasibility of laser-induced fluorescence spectroscopy in a living blood-filled arterial system we performed fiberoptic laser-induced fluorescence spectroscopy in a rabbit model of focal femoral atherosclerosis. A laser-induced fluorescence spectroscopy score was derived from stepwise linear regression analysis of in-vitro spectra to distinguish normal aorta (score>0) from atherosclerotic femoral artery (score<0). A 400 u silica fiber, coupled to a helium cadmium laser and optical multichannel analyzer, was inserted through a 5F catheter to induce and record in-vivo fluorescence from femoral and aortoiliac arteries. Arterial spectra could be recorded in all animals (n=10: 5 occlusions, 5 stenoses). Blood spectra were of low intensity and were easily distinguished from arterial spectra. The scores (mean ± SEM) for the in-vivo spectra were -0.69 +/- 0.29 for artherosclerotic femoral, and +0.54 ±. 0.15 for normal aorta (p<.01 p=NS compared to in-vitro spectra). In-vitro, a fiber tip to tissue distance <50 u was necessary for adequate arterial LIFS in blood. At larger distances low intensity blood spectra were recorded (1/20 the intensity of tissue spectra). Thus, fiberoptic laser-induced fluorescence spectroscopy can be sucessfully performed in a blood filled artery provided the fiber tip is approximated to the tissue.

  2. A novel fluorescent retrograde neural tracer: cholera toxin B conjugated carbon dots

    NASA Astrophysics Data System (ADS)

    Zhou, Nan; Hao, Zeyu; Zhao, Xiaohuan; Maharjan, Suraj; Zhu, Shoujun; Song, Yubin; Yang, Bai; Lu, Laijin

    2015-09-01

    tracers. Electronic supplementary information (ESI) available: PL spectra of CTB; absorption spectra of dialysate; fluorescence signal and immunohistochemical staining of CTB-CDs in L4 DRG. See DOI: 10.1039/c5nr04361a

  3. FIRST ULTRAVIOLET REFLECTANCE SPECTRA OF PLUTO AND CHARON BY THE HUBBLE SPACE TELESCOPE COSMIC ORIGINS SPECTROGRAPH: DETECTION OF ABSORPTION FEATURES AND EVIDENCE FOR TEMPORAL CHANGE

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Stern, S. A.; Spencer, J. R.; Shinn, A.

    We have observed the mid-UV spectra of both Pluto and its large satellite, Charon, at two rotational epochs using the Hubble Space Telescope (HST) Cosmic Origins Spectrograph (COS) in 2010. These are the first HST/COS measurements of Pluto and Charon. Here we describe the observations and our reduction of them, and present the albedo spectra, average mid-UV albedos, and albedo slopes we derive from these data. These data reveal evidence for a strong absorption feature in the mid-UV spectrum of Pluto; evidence for temporal change in Pluto's spectrum since the 1990s is reported, and indirect evidence for a near-UV spectralmore » absorption on Charon is also reported.« less

  4. Determination of adenosine disodium triphosphate (ATP) using oxytetracycline-Eu 3+ as a fluorescence probe by spectrofluorimetry

    NASA Astrophysics Data System (ADS)

    Hou, Faju; Miao, Yanhong; Jiang, Chongqiu

    2005-10-01

    A new spectrofluorimetric method was developed for determination of adenosine disodium triphosphate (ATP). We studied the interactions between oxytetracycline (OTC)-Eu 3+ complex and adenosine disodium triphosphate (ATP) by using UV-vis absorption and fluorescence spectra. Using oxytetracycline (OTC)-Eu 3+ as a fluorescence probe, under the optimum conditions, ATP can remarkably enhance the fluorescence intensity of the OTC-Eu 3+ complex at λ = 612 nm and the enhanced fluorescence intensity of Eu 3+ ion is in proportion to the concentration of ATP. Optimum conditions for the determination of ATP were also investigated. The linear ranges for ATP are 8.00 × 10 -8-1.50 × 10 -6 mol L -1 with detection limits of 2.67 × 10 -9 mol L -1. This method is simple, practical and relatively free interference from coexisting substances and can be successfully applied to determination of ATP in samples. The mechanism of fluorescence enhancement between oxytetracycline (OTC)-Eu 3+ complex and ATP was also studied.

  5. Investigation on the pH-dependent binding of benzocaine and lysozyme by fluorescence and absorbance.

    PubMed

    Li, Shihui; Li, Daojin

    2011-11-01

    The interaction mechanism between benzocaine (BZC) and lysozyme (Lys) has been investigated by fluorescence, synchronous fluorescence, ultraviolet-vis (UV) absorption spectra, and three-dimensional fluorescence (3-D) in various pH medium. The observations of fluorescence spectra were mainly rationalized in terms of a static quenching process at lower concentration of BZC (C(BZC)/C(Lys)<9) and a combined quenching process at higher concentration of BZC (C(BZC)/C(Lys)>9) at pH 7.4 and 8.4. However, the fluorescence quenching was mainly arisen from static quenching by complex formation in all studied drug concentrations at pH 3.5. The structural characteristics of BZC and Lys were probed, and their binding affinities were determined under different pH conditions (pH 3.5, 7.4, and 8.4). The results indicated that the binding abilities of BZC to Lys decreased at the pH below and above the simulative physiological condition (pH 7.4) due to the alterations of the protein secondary and tertiary structures or the structural change of BZC. The effect of BZC on the conformation of Lys was analyzed using UV, synchronous fluorescence and three-dimensional fluorescence under different pH conditions. These results indicate that the binding of BZC to Lys causes apparent change in the secondary and tertiary structures of Lys. The effect of Zn(2+) on the binding constant of BZC with Lys under various pH conditions (pH 3.5, 7.4, and 8.4) was also studied. Copyright © 2011 Elsevier B.V. All rights reserved.

  6. Spectral dependence of fluorescence near plasmon resonant metal nanoparticles

    NASA Astrophysics Data System (ADS)

    Chen, Yeechi

    The optical properties of fluorophores are significantly modified when placed within the near field (0--100 nm) of plasmon resonant metal nanostructures, due to the competition between increased decay rates and "hotspots" of concentrated electric fields. The decay rates and effective electric field intensities are highly dependent on the relative position of dye and metal and the overlap between plasmon resonance and dye absorption and emission. Understanding these dependencies can greatly improve the performance of biosensing and nanophotonic devices. In this dissertation, the fluorescence intensity of organic dyes and CdSe quantum dots near single metal nanoparticles is studied as a function of the local surface plasmon resonance (LSPR) of the nanoparticle. Single metal nanoparticles have narrow, well-defined, intense local surface plasmon resonances that are tunable across the visible spectrum by changes in size and shape. First, we show that organic dyes can be self-assembled on single silver nanoprisms into known configurations by the hybridization of thiolated DNA oligomers. We correlate the fluorescence intensity of the dyes to the LSPR of the individual nanoprism to which they are attached. For each of three different organic dyes, we observe a strong correlation between the fluorescence intensity of the dye and the degree of spectral overlap with the plasmon resonance of the nanoparticle. On average, we observe the brightest fluorescence from dyes attached to metal nanoparticles that have a LSPR scattering peak 40--120 meV higher in energy than the emission peak of the fluorophore. Second, the plasmon-enhanced fluorescence from CdSe/CdS/CdZnS/ZnS core/shell quantum dots is studied near a variety of silver and gold nanoparticles. With single-particle scattering spectroscopy, the localized surface plasmon resonance spectra of single metal nanoparticles is correlated with the photoluminescence excitation (PLE) spectra of the nearby quantum dots. The PLE

  7. C IV broad absorption line variability in QSO spectra from SDSS surveys

    NASA Astrophysics Data System (ADS)

    De Cicco, Demetra; Brandt, William N.; Grier, Catherine J.; Paolillo, Maurizio

    2017-12-01

    Broad absorption lines (BALs) in the spectra of quasi-stellar objects (QSOs) are thought to arise from outflowing winds along our line of sight; winds, in turn, are thought to originate from the accretion disk, in the very surroundings of the central supermassive black hole (SMBH), and they likely affect the accretion process onto the SMBH, as well as galaxy evolution. BALs can exhibit variability on timescales typically ranging from months to years. We analyze such variability and, in particular, BAL disappearance, with the aim of investigating QSO physics and structure. We search for disappearing C IV BALs in the spectra of 1319 QSOs from different programs from the Sloan Digital Sky Survey (SDSS); the analyzed time span covers 0.28-4.9 yr (rest frame), and the source redshifts are in the range 1.68-4.27. This is to date the largest sample ever used for such a study. We find 67 sources (5.1_{-0.6}^{+0.7}% of the sample) with 73 disappearing BALs in total (3.9_{-0.5}^{+0.5}% of the total number of C IV BALs detected; some sources have more than one BAL that disappears). We compare the sample of disappearing BALs to the whole sample of BALs, and investigate the correlation in the variability of multiple troughs in the same spectrum. We also derive estimates of the average lifetime of a BAL trough and of the BAL phase along our line of sight.

  8. Cost and sensitivity of restricted active-space calculations of metal L-edge X-ray absorption spectra.

    PubMed

    Pinjari, Rahul V; Delcey, Mickaël G; Guo, Meiyuan; Odelius, Michael; Lundberg, Marcus

    2016-02-15

    The restricted active-space (RAS) approach can accurately simulate metal L-edge X-ray absorption spectra of first-row transition metal complexes without the use of any fitting parameters. These characteristics provide a unique capability to identify unknown chemical species and to analyze their electronic structure. To find the best balance between cost and accuracy, the sensitivity of the simulated spectra with respect to the method variables has been tested for two models, [FeCl6 ](3-) and [Fe(CN)6 ](3-) . For these systems, the reference calculations give deviations, when compared with experiment, of ≤1 eV in peak positions, ≤30% for the relative intensity of major peaks, and ≤50% for minor peaks. When compared with these deviations, the simulated spectra are sensitive to the number of final states, the inclusion of dynamical correlation, and the ionization potential electron affinity shift, in addition to the selection of the active space. The spectra are less sensitive to the quality of the basis set and even a double-ζ basis gives reasonable results. The inclusion of dynamical correlation through second-order perturbation theory can be done efficiently using the state-specific formalism without correlating the core orbitals. Although these observations are not directly transferable to other systems, they can, together with a cost analysis, aid in the design of RAS models and help to extend the use of this powerful approach to a wider range of transition metal systems. © 2015 Wiley Periodicals, Inc.

  9. Soft x-ray absorption spectroscopy of metalloproteins and high-valent metal-complexes at room temperature using free-electron lasers

    PubMed Central

    Kubin, Markus; Kern, Jan; Gul, Sheraz; Kroll, Thomas; Chatterjee, Ruchira; Löchel, Heike; Fuller, Franklin D.; Sierra, Raymond G.; Quevedo, Wilson; Weniger, Christian; Rehanek, Jens; Firsov, Anatoly; Laksmono, Hartawan; Weninger, Clemens; Alonso-Mori, Roberto; Nordlund, Dennis L.; Lassalle-Kaiser, Benedikt; Glownia, James M.; Krzywinski, Jacek; Moeller, Stefan; Turner, Joshua J.; Minitti, Michael P.; Dakovski, Georgi L.; Koroidov, Sergey; Kawde, Anurag; Kanady, Jacob S.; Tsui, Emily Y.; Suseno, Sandy; Han, Zhiji; Hill, Ethan; Taguchi, Taketo; Borovik, Andrew S.; Agapie, Theodor; Messinger, Johannes; Erko, Alexei; Föhlisch, Alexander; Bergmann, Uwe; Mitzner, Rolf; Yachandra, Vittal K.; Yano, Junko; Wernet, Philippe

    2017-01-01

    X-ray absorption spectroscopy at the L-edge of 3d transition metals provides unique information on the local metal charge and spin states by directly probing 3d-derived molecular orbitals through 2p-3d transitions. However, this soft x-ray technique has been rarely used at synchrotron facilities for mechanistic studies of metalloenzymes due to the difficulties of x-ray-induced sample damage and strong background signals from light elements that can dominate the low metal signal. Here, we combine femtosecond soft x-ray pulses from a free-electron laser with a novel x-ray fluorescence-yield spectrometer to overcome these difficulties. We present L-edge absorption spectra of inorganic high-valent Mn complexes (Mn ∼ 6–15 mmol/l) with no visible effects of radiation damage. We also present the first L-edge absorption spectra of the oxygen evolving complex (Mn4CaO5) in Photosystem II (Mn < 1 mmol/l) at room temperature, measured under similar conditions. Our approach opens new ways to study metalloenzymes under functional conditions. PMID:28944255

  10. Soft x-ray absorption spectroscopy of metalloproteins and high-valent metal-complexes at room temperature using free-electron lasers

    DOE PAGES

    Kubin, Markus; Kern, Jan; Gul, Sheraz; ...

    2017-09-01

    X-ray absorption spectroscopy at the L-edge of 3d transition metals provides unique information on the local metal charge and spin states by directly probing 3d-derived molecular orbitals through 2p-3d transitions. But, this soft x-ray technique has been rarely used at synchrotron facilities for mechanistic studies of metalloenzymes due to the difficulties of x-ray-induced sample damage and strong background signals from light elements that can dominate the low metal signal. Here, we combine femtosecond soft x-ray pulses from a free-electron laser with a novel x-ray fluorescence-yield spectrometer to overcome these difficulties. We present L-edge absorption spectra of inorganic high-valent Mn complexesmore » (Mn ~ 6-15 mmol/l) with no visible effects of radiation damage. We then present the first L-edge absorption spectra of the oxygen evolving complex (Mn 4 CaO 5 ) in Photosystem II (Mn < 1 mmol/l) at room temperature, measured under similar conditions. Our approach opens new ways to study metalloenzymes under functional conditions.« less

  11. Absorption and fluorescence spectroscopic characterisation of the circadian blue-light photoreceptor cryptochrome from Drosophila melanogaster (dCry)

    NASA Astrophysics Data System (ADS)

    Shirdel, J.; Zirak, P.; Penzkofer, A.; Breitkreuz, H.; Wolf, E.

    2008-09-01

    The absorption and fluorescence behaviour of the circadian blue-light photoreceptor cryptochrome from Drosophila melanogaster (dCry) in a pH 8 aqueous buffer solution is studied. The flavin adenine dinucleotide (FAD) cofactor of dCry is identified to be present in its oxidized form (FAD ox), and the 5,10-methenyltetrahydrofolate (MTHF) cofactor is found to be hydrolyzed and oxidized to 10-formyldihydrofolate (10-FDHF). The absorption and the fluorescence behaviour of dCry is investigated in the dark-adapted (receptor) state, the light-adapted (signalling) state, and under long-time violet light exposure. Photo-excitation of FAD ox in dCry causes a reductive electron transfer to the formation of anionic FAD semiquinone (FAD rad - ), and photo-excitation of the generated FAD rad - causes an oxidative electron transfer to the back formation of FAD ox. In light adapted dCry a photo-induced equilibrium between FAD ox and FAD rad - exists. The photo-cycle dynamics of signalling state formation and recovery is discussed. Quantum yields of photo-induced signalling state formation of about 0.2 and of photo-induced back-conversion of about 0.2 are determined. A recovery of FAD rad - to FAD ox in the dark with a time constant of 1.6 min at room temperature is found.

  12. Absorption spectra of 4f electron transitions of neodymium and erbium with 8-hydroxyquinoline-5-sulphonic acid and diethylamine systems and its analytical application

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Wang Naixing; Qi Ping

    1992-06-01

    In this paper the absorption spectra of 4f electron transitions of the systems of neodymium and erbium with 8-hydroxyquinoline-5-sulphonic acid and diethylamine have been studied by normal and third-derivative spectrophotometry. Their molar absorptivities are 80 1.mol{sup {minus}1}.cm{sup {minus}1} for neodymium and 65 1.mol{sup {minus}1}.cm{sup {minus}1} for erbium. Use of the third-derivative spectra, eliminates the interference by other rare earths and increases the sensitivity for Nd and Er. The derivative molar absorptivities are 390 1.mol{sup {minus}1}.cm{sup {minus}1} for Nd and 367 1.mol{sup {minus}1}.cm{sup {minus}1} for Er. The calibration graphs were linear up to 11.8 {mu}g/ml of Nd and 12.3 {mu}g/ml ofmore » Er, respectively. The relative standard deviations evaluated from eleven independent determinations of 7.2 {mu}g/ml (for Nd) and 8.3 {mu}g/ml (for Er) are 1.3% and 1.4%, respectively. The detection limits are 0.2 {mu}g/ml for Nd and 0.3 {mu}g/ml for Er. The method has been developed for determining those two elements in mixture of lanthanides by means of the third-derivative spectra and the analytical results obtained are satisfactory.« less

  13. Fluorenyl benzothiadiazole and benzoselenadiazole near-IR fluorescent probes for two-photon fluorescence imaging (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Belfield, Kevin D.; Yao, Sheng; Kim, Bosung; Yue, Xiling

    2016-03-01

    Imaging biological samples with two-photon fluorescence (2PF) microscopy has the unique advantage of resulting high contrast 3D resolution subcellular image that can reach up to several millimeters depth. 2PF probes that absorb and emit at near IR region need to be developed. Two-photon excitation (2PE) wavelengths are less concerned as 2PE uses wavelengths doubles the absorption wavelength of the probe, which means 2PE wavelengths for probes even with absorption at visible wavelength will fall into NIR region. Therefore, probes that fluoresce at near IR region with high quantum yields are needed. A series of dyes based on 5-thienyl-2, 1, 3-benzothiadiazole and 5-thienyl-2, 1, 3-benzoselenadiazole core were synthesized as near infrared two-photon fluorophores. Fluorescence maxima wavelengths as long as 714 nm and fluorescence quantum yields as high as 0.67 were achieved. The fluorescence quantum yields of the dyes were nearly constant, regardless of solvents polarity. These diazoles exhibited large Stokes shift (<114nm), high two-photon absorption cross sections (up to 2,800 GM), and high two-photon fluorescence figure of merit (FM , 1.04×10-2 GM). Cells incubated on a 3D scaffold with one of the new probes (encapsulated in Pluronic micelles) exhibited bright fluorescence, enabling 3D two-photon fluorescence imaging to a depth of 100 µm.

  14. Infrared Measurements of Atmospheric Ethane (C2H6) From Aircraft and Ground-Based Solar Absorption Spectra in the 3000/ cm Region

    NASA Technical Reports Server (NTRS)

    Coffey, M. T.; Mankin, W. G.; Goldman, A.; Rinsland, C. P.; Harvey, G. A.; Devi, V. Malathy; Stokes, G. M.

    1985-01-01

    A number or prominent Q-branches or the upsilon(sub 7) band or C2H6 have been identified near 3000/ cm in aircraft and ground-based infrared solar absorption spectra. The aircraft spectra provide the column amount above 12 km at various altitudes. The column amount is strongly correlated with tropopause height and can be described by a constant mixing ratio of 0.46 ppbv in the upper troposphere and a mixing ratio scale height of 3.9 km above the tropopause. The, ground-based spectra yield a column of 9.0 x 10(exp 15) molecules/sq cm above 2.1 km; combining these results implies a tropospheric mixing ratio of approximately 0.63 ppbv.

  15. Infrared measurements of atmospheric ethane (C2H6) from aircraft and ground-based solar absorption spectra in the 3000/cm region

    NASA Technical Reports Server (NTRS)

    Coffey, M. T.; Mankin, W. G.; Goldman, A.; Rinsland, C. P.; Harvey, G. A.; Devi, V. M.; Stokes, G. M.

    1985-01-01

    A number of prominent Q-branches of the nu-7 band of C2H6 have been identified near 3000/cm in aircraft and ground-based infrared solar absorption spectra. The aircraft spectra provide the column amount above 12 km at various altitudes. The column amount is strongly correlated with tropopause height and can be described by a constant mixing ratio of 0.46 ppbv in the upper troposphere and a mixing ratio scale height of 3.9 km above the tropopause. The ground-based spectra yield a column of 9.0 x 10 to the 15th molecules/sq cm above 2.1 km; combining these results implies a tropospheric mixing ratio of approximately 0.63 ppbv.

  16. Hydroxylated Fluorescent Dyes for Live‐Cell Labeling: Synthesis, Spectra and Super‐Resolution STED†

    PubMed Central

    Kolmakov, Kirill; Sokolov, Viktor V.; Shojaei, Heydar; Sidenstein, Sven C.; Kamin, Dirk; Matthias, Jessica; Vlijm, Rifka; Engelhardt, Johann

    2017-01-01

    Abstract 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 for prediction of the spectral properties and the positions of spirolactone/zwitterion equilibria for the new analogues of rhodamines, carbo‐, silico‐, and germanorhodamines using simple additive schemes. PMID:28370443

  17. Excitation energy dependence of excited states dynamics in all- trans-carotenes determined by femtosecond absorption and fluorescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Kosumi, Daisuke; Yanagi, Kazuhiro; Nishio, Tomohiro; Hashimoto, Hideki; Yoshizawa, Masayuki

    2005-06-01

    Ultrafast relaxation kinetics in β-carotene and lycopene has been investigated by femtosecond absorption and fluorescence spectroscopies using tunable excitation pulses. The transient signals induced by the photoexcitation with larger excess energy have broader bands and longer lifetimes both in the 11Bu+and21Ag- excited states. The excess vibrational energy remains longer than several picoseconds and slows the relaxation kinetics in carotenoids.

  18. Molecular specificity in photoacoustic microscopy by time-resolved transient absorption.

    PubMed

    Shelton, Ryan L; Mattison, Scott P; Applegate, Brian E

    2014-06-01

    We have recently harnessed transient absorption, a resonant two-photon process, for ultrahigh resolution photoacoustic microscopy, achieving nearly an order of magnitude improvement in axial resolution. The axial resolution is optically constrained due to the two-photon process unlike traditional photoacoustic microscopy where the axial resolution is inversely proportional to the frequency bandwidth of the detector. As a resonant process, the arrival time of the two photons need not be instantaneous. Systematically recording the signal as a function of the delay between two pulses will result in the measurement of an exponential decay whose time constant is related to the molecular dynamics. This time constant, analogous to the fluorescence lifetime, but encompassing nonradiative decay as well, can be used to differentiate between molecular systems with overlapping absorption spectra. This is frequently the situation for closely related yet distinct molecules such as redox pairs. In order to enable the measure of the exponential decay, we have reconfigured our transient absorption ultrasonic microscopy (TAUM) system to incorporate two laser sources with precisely controlled pulse trains. The system was tested by measuring Rhodamine 6G, an efficient laser dye where the molecular dynamics are dominated by the fluorescence pathway. As expected, the measured exponential time constant or ground state recovery time, 3.3±0.7  ns, was similar to the well-known fluorescence lifetime, 4.11±0.05  ns. Oxy- and deoxy-hemoglobin are the quintessential pair whose relative concentration is related to the local blood oxygen saturation. We have measured the ground state recovery times of these two species in fully oxygenated and deoxygenated bovine whole blood to be 3.7±0.8  ns and 7.9±1.0  ns, respectively. Hence, even very closely related pairs of molecules may be differentiated with this technique.

  19. Complex polarization propagator approach in the restricted open-shell, self-consistent field approximation: the near K-edge X-ray absorption fine structure spectra of allyl and copper phthalocyanine.

    PubMed

    Linares, Mathieu; Stafström, Sven; Rinkevicius, Zilvinas; Ågren, Hans; Norman, Patrick

    2011-05-12

    A presentation of the complex polarization propagator in the restricted open-shell self-consistent field approximation is given. It rests on a formulation of a resonant-convergent, first-order polarization propagator approach that makes it possible to directly calculate the X-ray absorption cross section at a particular frequency without explicitly addressing the excited states. The quality of the predicted X-ray spectra relates only to the type of density functional applied without any separate treatment of dynamical relaxation effects. The method is applied to the calculation of the near K-edge X-ray absorption fine structure spectra of allyl and copper phthalocyanine. Comparison is made between the spectra of the radicals and those of the corresponding cations and anions to assess the effect of the increase of electron charge in the frontier orbital. The method offers the possibility for unique assignment of symmetry-independent atoms. The overall excellent spectral agreement motivates the application of the method as a routine precise tool for analyzing X-ray absorption of large systems of technological interest.

  20. The Rovibronic Spectra of the Cyclopentadienyl Radical

    NASA Astrophysics Data System (ADS)

    Sharma, Ketan; Miller, Terry A.; Stanton, John F.; Nesbitt, David

    2017-06-01

    Cyclopentadienyl (Cp) radical has been subject to numerous studies for the greater part of half a century. Experimental work has involved photo-electron spectroscopy, laser induced fluorescence excitation and emission, infrared absorption spectroscopy, and recently rotationally resolved spectra in the CH stretch region taken at JILA. Even more theoretical works appear in the literature, but substantial advances in computation have occurred since their completion. Cp's highly symmetric (D_{5h}) structure and doubly degenerate electronic ground (˜{X}^2E_1^{''}), which is subject to linear Jahn-Teller distortion, have been a great motivation for work on it. We have commenced new computational work to obtain a broad understanding of the electronic, vibrational, and rotational, i.e. rovibronic, structure of the Cp radical as revealed by its spectra, with particular emphasis on the new infrared spectra. The goal is to guide experiments and their analyses and reconcile results from spectroscopy and quantum chemistry calculations. T. Ichino, et al. J. Chem. Phys. 129, 084310 (2008) L. Yu, S. C. Foster, J. M. Williamson, M. C. Heaven and T. A. Miller J. Phys. Chem. 92, 4263 (1988) B. E. Applegate, A. J. Bezant and T. A. Miller J. Chem. Phys 114, 4869 (2001) D. Leicht, M. Kaufmann, G. Schwaab, and M. Havenith J. Chem. Phys. 145, 7 (2016), 074304.

  1. Foliar Reflectance and Fluorescence Responses for Plants Under Nitrogen Stress Determined with Active and Passive Systems

    NASA Technical Reports Server (NTRS)

    Middleton, E. M.; McMurtrey, J. E.; Campbell, P. K. Entcheva; Corp, L. A.; Butcher, L. M.; Chappelle, E. W.

    2003-01-01

    Vegetation productivity is driven by nitrogen (N) availability in soils. Both excessive and low soil N induce physiological changes in plant foliage. In 2001, we examined the use of spectral fluorescence and reflectance measurements to discriminate among plants provided different N fertilizer application rates: 20%, 50%, 100% and 150% of optimal N levels. A suite of optical, fluorescence, and biophysical measurements were collected on leaves from field grown corn (Zea mays L.) and soybean plants (Glycine max L.) grown in pots (greenhouse + ambient sunlight daily). Three types of steady state laser-induced fluorescence measurements were made on adaxial and abaxial surfaces: 1) fluorescence images in four 10 nm bands (blue, green, red, far-red) resulting from broad irradiance excitation; 2) emission spectra (5 nm resolution) produced by excitation at single wavelengths (280,380 or 360, and 532 nm); and 3) excitation spectra (2 nm resolution), with emission wavelengths fixed at wavelengths centered on selected solar Fraunhofer lines (532,607,677 and 745 nm). Two complementary sets of high resolution (less than 2 nm) optical spectra were acquired for both adaxial and abaxial leaf surfaces: 1) optical properties (350-2500 nm) for reflectance, transmittance, and absorptance; and 2) reflectance spectra (500-1000 nm) acquired with and without a short pass filter at 665 nm to determine the fluorescence contribution to apparent reflectance in the 650-750 spectrum, especially at the 685 and 740 nm chlorophyll fluorescence (ChIF) peaks. The strongest relationships between foliar chemistry and optical properties were demonstrated for C/N content and two optical parameters associated with the red edge inflection point. Select optical properties and ChIF parameters were highly correlated for both species. A significant contribution of ChIF to apparent reflectance was observed, averaging 10-25% at 685 nm and 2 - 6% at 740 nm over all N treatments. Discrimination of N treatment

  2. a Model to Simulate the Radiative Transfer of Fluorescence in a Leaf

    NASA Astrophysics Data System (ADS)

    Zhao, F.; Ni, Q.

    2018-04-01

    Light is reflected, transmitted and absorbed by green leaves. Chlorophyll fluorescence (ChlF) is the signal emitted by chlorophyll molecules in the leaf after the absorption of light. ChlF can be used as a direct probe of the functional status of photosynthetic machinery because of its close relationship with photosynthesis. The scattering, absorbing, and emitting properties of leaves are spectrally dependent, which can be simulated by modeling leaf-level fluorescence. In this paper, we proposed a Monte-Carlo (MC) model to simulate the radiative transfer of photons in the leaf. Results show that typical leaf fluorescence spectra can be properly simulated, with two peaks centered at around 685 nm in the red and 740 nm in the far-red regions. By analysing the sensitivity of the input parameters, we found the MC model can well simulate their influence on the emitted fluorescence. Meanwhile we compared results simulated by MC model with those by the Fluspect model. Generally they agree well in the far-red region but deviate in the red region.

  3. Restricted active space calculations of L-edge X-ray absorption spectra: from molecular orbitals to multiplet states.

    PubMed

    Pinjari, Rahul V; Delcey, Mickaël G; Guo, Meiyuan; Odelius, Michael; Lundberg, Marcus

    2014-09-28

    The metal L-edge (2p → 3d) X-ray absorption spectra are affected by a number of different interactions: electron-electron repulsion, spin-orbit coupling, and charge transfer between metal and ligands, which makes the simulation of spectra challenging. The core restricted active space (RAS) method is an accurate and flexible approach that can be used to calculate X-ray spectra of a wide range of medium-sized systems without any symmetry constraints. Here, the applicability of the method is tested in detail by simulating three ferric (3d(5)) model systems with well-known electronic structure, viz., atomic Fe(3+), high-spin [FeCl6](3-) with ligand donor bonding, and low-spin [Fe(CN)6](3-) that also has metal backbonding. For these systems, the performance of the core RAS method, which does not require any system-dependent parameters, is comparable to that of the commonly used semi-empirical charge-transfer multiplet model. It handles orbitally degenerate ground states, accurately describes metal-ligand interactions, and includes both single and multiple excitations. The results are sensitive to the choice of orbitals in the active space and this sensitivity can be used to assign spectral features. A method has also been developed to analyze the calculated X-ray spectra using a chemically intuitive molecular orbital picture.

  4. Infrared absorption spectra of N(CxF2x+1)3, x = 2-5 perfluoroamines

    NASA Astrophysics Data System (ADS)

    Bernard, François; Papanastasiou, Dimitrios K.; Papadimitriou, Vassileios C.; Burkholder, James B.

    2018-05-01

    Infrared absorption spectra of the perfluoroamines (N(C2F5)3, N(C3F7)3, N(C4F9)3, and N(C5F11)3) were measured over the 500-4000 cm-1 spectral region at 294 K using Fourier transform infrared (FTIR) spectroscopy at 1 cm-1 resolution. Spectral measurements were performed using static measurements of dilute perfluoroamines mixtures and by infusion of the pure compound into a calibrated gas flow. The perfluoroamines absorb strongly in the "atmospheric window" with integrated band strengths (10-17 cm2 molecule-1 cm-1) between 570 and 1500 cm-1 of 59.9, 74.9, 88.9, and 98.7 for N(C2F5)3, N(C3F7)3, N(C4F9)3, and N(C5F11)3, respectively. Radiative efficiencies (RE) for the perfluoroamines were estimated to be 0.61, 0.75, 0.87, and 0.95 W m-2 ppb-1 for atmospherically well-mixed conditions and including a +10% stratospheric temperature correction for N(C2F5)3, N(C3F7)3, N(C4F9)3, and N(C5F11)3, respectively. Theoretical calculations of the perfluoroamines were performed at the B97-1/6-311++G(2df,2p) level of theory and optimized perfluoroamine geometries, vibrational band positions, and band strengths are reported. The theoretically calculated infrared spectra are in good agreement with the experimental spectra, while comparison of individual bands was not attempted due to the significant overlap of vibrational bands in the experimental spectra.

  5. Resonant two-photon ionization and laser induced fluorescence spectroscopy of jet-cooled adenine

    NASA Astrophysics Data System (ADS)

    Kim, Nam Joon; Jeong, Gawoon; Kim, Yung Sam; Sung, Jiha; Keun Kim, Seong; Park, Young Dong

    2000-12-01

    Electronic spectra of the jet-cooled DNA base adenine were obtained by the resonant two-photon ionization (R2PI) and the laser induced fluorescence (LIF) techniques. The 0-0 band to the lowest electronically excited state was found to be located at 35 503 cm-1. Well-resolved vibronic structures were observed up to 1100 cm-1 above the 0-0 level, followed by a slow rise of broad structureless absorption. The lowest electronic state was proposed to be of nπ* character, which lies ˜600 cm-1 below the onset of the ππ* state. The broad absorption was attributed to the extensive vibronic mixing between the nπ* state and the high-lying ππ* state.

  6. Substituent and solvent effects on electronic spectra of some substituted phenoxyacetic acids.

    PubMed

    Shanthi, M; Kabilan, S

    2007-06-01

    The effects of substituents and solvents have been studied through the absorption spectra of nearly 19 para- and ortho-substituted phenoxyacetic acids in the range of 200-400 nm. The effects of substituent on the absorption spectra of compounds under present investigation are interpreted by correlation of absorption frequencies with simple and extended Hammett equations. Effect of solvent polarity and hydrogen bonding on the absorption spectra are interpreted by means of Kamlet equation and the results are discussed.

  7. Substituent and solvent effects on electronic spectra of some substituted phenoxyacetic acids

    NASA Astrophysics Data System (ADS)

    Shanthi, M.; Kabilan, S.

    2007-06-01

    The effects of substituents and solvents have been studied through the absorption spectra of nearly 19 para- and ortho-substituted phenoxyacetic acids in the range of 200-400 nm. The effects of substituent on the absorption spectra of compounds under present investigation are interpreted by correlation of absorption frequencies with simple and extended Hammett equations. Effect of solvent polarity and hydrogen bonding on the absorption spectra are interpreted by means of Kamlet equation and the results are discussed.

  8. Photobleaching response of different sources of chromophoric dissolved organic matter exposed to natural solar radiation using absorption and excitation-emission matrix spectra.

    PubMed

    Zhang, Yunlin; Liu, Xiaohan; Osburn, Christopher L; Wang, Mingzhu; Qin, Boqiang; Zhou, Yongqiang

    2013-01-01

    CDOM biogeochemical cycle is driven by several physical and biological processes such as river input, biogeneration and photobleaching that act as primary sinks and sources of CDOM. Watershed-derived allochthonous (WDA) and phytoplankton-derived autochthonous (PDA) CDOM were exposed to 9 days of natural solar radiation to assess the photobleaching response of different CDOM sources, using absorption and fluorescence (excitation-emission matrix) spectroscopy. Our results showed a marked decrease in total dissolved nitrogen (TDN) concentration under natural sunlight exposure for both WDA and PDA CDOM, indicating photoproduction of ammonium from TDN. In contrast, photobleaching caused a marked increase in total dissolved phosphorus (TDP) concentration for both WDA and PDA CDOM. Thus TDN:TDP ratios decreased significantly both for WDA and PDA CDOM, which partially explained the seasonal dynamic of TDN:TDP ratio in Lake Taihu. Photobleaching rate of CDOM absorption a(254), was 0.032 m/MJ for WDA CDOM and 0.051 m/MJ for PDA CDOM from days 0-9, indicating that phototransformations were initially more rapid for the newly produced CDOM from phytoplankton than for the river CDOM. Extrapolation of these values to the field indicated that 3.9%-5.1% CDOM at the water surface was photobleached and mineralized every day in summer in Lake Taihu. Photobleaching caused the increase of spectral slope, spectral slope ratio and molecular size, indicating the CDOM mean molecular weight decrease which was favorable to further microbial degradation of mineralization. Three fluorescent components were validated in parallel factor analysis models calculated separately for WDA and PDA CDOM. Our study suggests that the humic-like fluorescence materials could be rapidly and easily photobleached for WDA and PDA CDOM, but the protein-like fluorescence materials was not photobleached and even increased from the transformation of the humic-like fluorescence substance to the protein

  9. Photobleaching Response of Different Sources of Chromophoric Dissolved Organic Matter Exposed to Natural Solar Radiation Using Absorption and Excitation–Emission Matrix Spectra

    PubMed Central

    Zhang, Yunlin; Liu, Xiaohan; Osburn, Christopher L.; Wang, Mingzhu; Qin, Boqiang; Zhou, Yongqiang

    2013-01-01

    CDOM biogeochemical cycle is driven by several physical and biological processes such as river input, biogeneration and photobleaching that act as primary sinks and sources of CDOM. Watershed-derived allochthonous (WDA) and phytoplankton-derived autochthonous (PDA) CDOM were exposed to 9 days of natural solar radiation to assess the photobleaching response of different CDOM sources, using absorption and fluorescence (excitation-emission matrix) spectroscopy. Our results showed a marked decrease in total dissolved nitrogen (TDN) concentration under natural sunlight exposure for both WDA and PDA CDOM, indicating photoproduction of ammonium from TDN. In contrast, photobleaching caused a marked increase in total dissolved phosphorus (TDP) concentration for both WDA and PDA CDOM. Thus TDN∶TDP ratios decreased significantly both for WDA and PDA CDOM, which partially explained the seasonal dynamic of TDN∶TDP ratio in Lake Taihu. Photobleaching rate of CDOM absorption a(254), was 0.032 m/MJ for WDA CDOM and 0.051 m/MJ for PDA CDOM from days 0–9, indicating that phototransformations were initially more rapid for the newly produced CDOM from phytoplankton than for the river CDOM. Extrapolation of these values to the field indicated that 3.9%–5.1% CDOM at the water surface was photobleached and mineralized every day in summer in Lake Taihu. Photobleaching caused the increase of spectral slope, spectral slope ratio and molecular size, indicating the CDOM mean molecular weight decrease which was favorable to further microbial degradation of mineralization. Three fluorescent components were validated in parallel factor analysis models calculated separately for WDA and PDA CDOM. Our study suggests that the humic-like fluorescence materials could be rapidly and easily photobleached for WDA and PDA CDOM, but the protein-like fluorescence materials was not photobleached and even increased from the transformation of the humic-like fluorescence substance to the protein

  10. Multiphoton-gated cycloreversion reaction of a fluorescent diarylethene derivative as revealed by transient absorption spectroscopy.

    PubMed

    Nagasaka, Tatsuhiro; Kunishi, Tomohiro; Sotome, Hikaru; Koga, Masafumi; Morimoto, Masakazu; Irie, Masahiro; Miyasaka, Hiroshi

    2018-06-07

    The one- and two-photon cycloreversion reactions of a fluorescent diarylethene derivative with oxidized benzothiophene moieties were investigated by means of ultrafast laser spectroscopy. Femtosecond transient absorption spectroscopy under the one-photon excitation condition revealed that the excited closed-ring isomer is simply deactivated into the initial ground state with a time constant of 2.6 ns without remarkable cycloreversion, the results of which are consistent with the very low cycloreversion reaction yield (<10-5) under steady-state light irradiation. On the other hand, an efficient cycloreversion reaction was observed under irradiation with a picosecond laser pulse at 532 nm. The excitation intensity dependence of the cycloreversion reaction indicates that a highly excited state attained by the stepwise two-photon absorption is responsible for the marked increase of the cycloreversion reaction, and the quantum yield at the highly excited state was estimated to be 0.018 from quantitative analysis, indicating that the reaction is enhanced by a factor of >1800.

  11. 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.

  12. [Seasonal variation in the absorption and fluorescence characteristics of CDOM in downstream of Liaohe River].

    PubMed

    Shao, Tian-Tian; Zhao, Ying; Song, Kai-Shan; Du, Jia; Ding, Zhi

    2014-10-01

    Chromophoric dissolved organic matter (CDOM), which is an important part of dissolved organic matter (DOM), is considered as the largest storage of dissolved organic carbon in the aquatic environment. Liaohe River is the seventh largest river in China with annual runoff of 1.48 billion m3. As a result, studying on CDOM of Liaohe River is very important in estimating the organic carbon flux into sea. Seasonal optical characteristics of CDOM in the downstream of Liaohe River were investigated using absorbance spectroscopy and fluorescence excitation-emission matrices (EEMs). CDOM absorption coefficient at 355 nm [aCDOM (355)] in spring was lower than that in autumn and winter while low molecular weight substances were found in autumn and high molecular weight substances in spring based on the absorption coefficient and absorption slope (S) of CDOM. Samples in different seasons all exhibited fairly strong protein-like fluorophore (fluorophore B and fluorophore T) in the EEMs but the values showed apparent temporal variations. Based on the analysis of the relationships between different fluorophores, strong correlations (R2 > 0. 9) were observed between fluorophore A and C in spring, fluorophore B and T in autumn and winter, which illustrated that they had similar CDOM originalsources. However, a weak relationship (R2 = 0.21) was found between fluorophore B and T in spring, demonstrating the complexity and diversity of CDOM sources. Starting from autumn to winter and the subsequent spring, humic-like fluorophores exhibited enhanced fluorescent intensity, which could be ascribed to exogenous input. Furthermore, linear relationship between aCDOM (355) and Fn (355) in different seasons was examined in the study, and the strongest relationship was obtained in winter (R2 = 0.75), followed by autumn (R2 = 0.48) and spring (R2 = 0.01). This study indicated that fluorophore B in autumn and winter (R = 0.66; R = 0.89) as well as humic-like fluorophores (A and C, R = 0.74; R = 0

  13. Circular dichroism and optical absorption spectra of mononuclear and trinuclear chiral Cu(II) amino-alcohol coordinated compounds: A combined theoretical and experimental study

    NASA Astrophysics Data System (ADS)

    Valencia, Israel; Ávila-Torres, Yenny; Barba-Behrens, Norah; Garzón, Ignacio L.

    2015-04-01

    Studies on the physicochemical properties of biomimetic compounds of multicopper oxidases are fundamental to understand their reaction mechanisms and catalytic behavior. In this work, electronic, optical, and chiroptical properties of copper(II) complexes with amino-alcohol chiral ligands are theoretically studied by means of time-dependent density functional theory. The calculated absorption and circular dichroism spectra are compared with experimental measurements of these spectra for an uncoordinated pseudoephedrine derivative, as well as for the corresponding mononuclear and trinuclear copper(II)-coordinated complexes. This comparison is useful to gain insights into their electronic structure, optical absorption and optical activity. The optical absorption and circular dichroism bands of the pseudoephedrine derivative are located in the UV-region. They are mainly due to transitions originated from n to π anti-bonding orbitals of the alcohol and amino groups, as well as from π bonding to π anti-bonding orbitals of carboxyl and phenyl groups. In the case of the mononuclear and trinuclear compounds, additional signals in the visible spectral region are present. In both systems, the origin of these bands is due to charge transfer from ligand to metal and d-d transitions.

  14. The HST-pNFL program: Mapping the Fluorescent Emission of Galactic Outflows

    NASA Astrophysics Data System (ADS)

    Heckman, Timothy

    2017-08-01

    Galactic outflows associated with star formation are believed to play a crucial role in the evolution of galaxies and the IGM. Most of our knowledge about outflows has come from down-the-barrel UV absorption spectroscopy of star-forming galaxies. However, absorption-line data alone provide only indirect information about the radial structure of the gas flows, which introduces large systematic uncertainties in some of the most important quantities, such as the outflow rate, the mass loading factor, and the momentum, metal, and energy fluxes. Recent spectroscopic observations of star-forming galaxies with large (projected physical) apertures have revealed non-resonant (fluorescent) emission in the UV, e.g., FeII* and SiII*, that can be naturally produced by spatially extended emission from the same outflowing material traced in absorption. Encouraged by the most recent observations of FeII* emission by the SDSS-IV/eBOSS survey (Zhu et al. 2015), we propose a pilot program to use narrow-band filter UVIS F280N images to map the extended FeII* 2626 and 2613 fluorescent emission in a carefully-chosen sample of 4 starburst galaxies at z=0.065, and COS G130M to obtain down-the- barrel spectra for SiII absorption and SiII* emission. This HST pilot program can provide unique information about the spatial structure of galactic outflows and can potentially lead to a revolution in our understanding of outflow physics and its impact on galaxies and the IGM.

  15. Optical Absorption Spectra of Hydrogenated Microcrystalline Silicon Films by Resonant Photothermal Bending Spectroscopy

    NASA Astrophysics Data System (ADS)

    Kunii, Toshie; Yoshida, Norimitsu; Hori, Yasuro; Nonomura, Shuichi

    2006-05-01

    A resonant photothermal bending spectroscopy (PBS) is demonstrated for the measurement of absorption coefficient spectra in hydrogenated microcrystalline silicon (μc-Si:H) and hydrogenated microcrystalline cubic silicon carbide (μc-3C-SiC:H) films. The resonant vibration technique utilized in PBS establishes the sensitivity as α d˜ 5× 10-5 in a vacuum measurement. Appling resonant PBS to μc-Si:H films, a new extra absorption coefficient αex spectrum is observed from 0.6 to 1.2 eV. The αex spectrum has a peak at ˜1.0 eV, and the localized states inducing the αex are located ˜0.35 eV below the conduction band edge of μc-Si:H. A possible explanation for the observed localized state is that an oxidation produces weak bonds at the grain boundaries and/or amorphous silicon tissues. In μc-3C-SiC:H film, an optical band-gap energy of ˜2.2 eV was demonstrated assuming an indirect optical transition. The temperature coefficient of the optical band-gap energy was ˜2.3× 10-4 eV K-1. The αex spectrum of μc-3C-SiC:H film is plateau-shaped and its magnitude is in accord with an increase in grain size.

  16. 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.

  17. Impact effects of gamma irradiation on the optical and FT infrared absorption spectra of some Nd3+-doped soda lime phosphate glasses

    NASA Astrophysics Data System (ADS)

    Marzouk, M. A.; Elkashef, I. M.; Elbatal, H. A.

    2018-04-01

    The main aim of the present work is to study by two collective optical and FTIR spectral measurements some prepared Nd2O3-doped soda lime phosphate glasses before and after gamma irradiation with dose (9 Mrad). The spectral data reveal two strong UV absorption peaks which are correlated with unavoidable trace iron impurities beside extended additional characteristic bands due to Nd3+ ions. Gamma irradiation on the undoped glass produces slight decrease of the intensity of the UV absorption and the generation of an induced visible band and these effects are controlled with two photochemical reduction of some Fe3+ ions to Fe2+ ions together with the formation of nonbridging oxygen hole center (NBOHC) or phosphorous oxygen hole center (POHC). The impact effect of gamma irradiation on the spectra of Nd2O3-doped glasses is limited due to suggested shielding behavior of neodymium ions. FT-infrared spectra show vibrational modes due to main Q2-Q3 phosphate groups and the response of gamma irradiation of the IR spectra is low and the limited variations are related to suggested changes in some bond angles and bond lengths which cause the observed decrease to the intensities of some IR bands.

  18. Anomalous doping of a molecular crystal monitored with confocal fluorescence microscopy: Terrylene in a p-terphenyl crystal

    NASA Astrophysics Data System (ADS)

    Białkowska, Magda; Deperasińska, Irena; Makarewicz, Artur; Kozankiewicz, Bolesław

    2017-09-01

    Highly terrylene doped single crystals of p-terphenyl, obtained by co-sublimation of both components, showed bright spots in the confocal fluorescence images. Polarization of the fluorescence excitation spectra, blinking and bleaching, and saturation behavior allowed us to attribute them to single molecules of terrylene anomalously embedded between two neighbor layers of the host crystal, in the (a,b) plane. Such an orientation of terrylene molecules results in much more efficient absorption and collection of the fluorescence photons than in the case of previously investigated molecules embedded in the substitution sites. The above conclusion was supported by quantum chemistry calculations. We postulate that the kind of doping considered in this work should be possible in other molecular crystals where the host molecules are organized in a herringbone pattern.

  19. Multiconfigurational and DFT analyses of the electromeric formulation and UV-vis absorption spectra of the superoxide adduct of ferrous superoxide reductase.

    PubMed

    Attia, Amr A A; Cioloboc, Daniela; Lupan, Alexandru; Silaghi-Dumitrescu, Radu

    2016-12-01

    The putative initial adduct of ferrous superoxide reductase (SOR) with superoxide has been alternatively formulated as ferric-peroxo or ferrous-superoxo. The ~600-nm UV-vis absorption band proposed to be assigned to this adduct (either as sole intermediate in the SOR catalytic cycle, or as one of the two intermediates) has recently been interpreted as due to a ligand-to-metal charge transfer, involving thiolate and superoxide in a ferrous complex, contrary to an alternative assignment as a predominantly cysteine thiolate-to-ferric charge transfer in a ferric-peroxo electromer. In an attempt to clarify the electromeric formulation of this adduct, we report a computational study using a multiconfigurational complete active space self-consistent field (MC-CASSCF) wave function approach as well as modelling the UV-vis absorption spectra with time-dependent density functional theory (TD-DFT). The MC-CASSCF calculations disclose a weak interaction between iron and the dioxygenic ligand and a dominant configuration with an essentially ferrous-superoxo character. The computed UV-vis absorption spectra reveal a marked dependence on the choice of density functional - both in terms of location of bands and in terms of orbital contributors. For the main band in the visible region, besides the recently reported thiolate-to-superoxide charge transfer, a more salient, and less functional-dependent, feature is a thiolate-to-ferric iron charge transfer, consistent with a ferric-peroxo electromer. By contrast, the computed UV-vis spectra of a ferric-hydroperoxo SOR model match distinctly better (and with no qualitative dependence on the DFT methodology) the 600-nm band as due to a mainly thiolate-to-ferric character - supporting the assignment of the SOR "600-nm intermediate" as a S=5/2 ferric-hydroperoxo species. Copyright © 2016 Elsevier Inc. All rights reserved.

  20. Application of Time-Dependent Density Functional and Natural Bond Orbital Theories to the UV-vis Absorption Spectra of Some Phenolic Compounds.

    PubMed

    Marković, Svetlana; Tošović, Jelena

    2015-09-03

    The UV-vis properties of 22 natural phenolic compounds, comprising anthraquinones, neoflavonoids, and flavonoids were systematically examined. The time-dependent density functional theory (TDDFT) approach in combination with the B3LYP, B3LYP-D2, B3P86, and M06-2X functionals was used to simulate the UV-vis spectra of the investigated compounds. It was shown that all methods exhibit very good (B3LYP slightly better) performance in reproducing the examined UV-vis spectra. However, the shapes of the Kohn-Sham molecular orbitals (MOs) involved in electronic transitions were misleading in constructing the MO correlation diagrams. To provide better understanding of redistribution of electron density upon excitation, the natural bond orbital (NBO) analysis was applied. Bearing in mind the spatial and energetic separations, as well as the character of the π bonding, lone pair, and π* antibonding natural localized molecular orbitals (NLMOs), the "NLMO clusters" were constructed. NLMO cluster should be understood as a part of a molecule characterized with distinguished electron density. It was shown that all absorption bands including all electronic transitions need to be inspected to fully understand the UV-vis spectrum of a certain compound, and, thus, to learn more about its UV-vis light absorption. Our investigation showed that the TDDFT and NBO theories are complementary, as the results from the two approaches can be combined to interpret the UV-vis spectra. Agreement between the predictions of the TDDFT approach and those based on the NLMO clusters is excellent in the case of major electronic transitions and long wavelengths. It should be emphasized that the approach for investigation of UV-vis light absorption based on the NLMO clusters is applied for the first time.