Laser-excited Shpol'skii spectroscopy for the selective excitation and determination of polynuclear aromatic hydrocarbons

Yang, Yen.; D’Silva, Arthur P.; Fassel, Velmer A.

doi:10.1021/ac00229a035

Cited by 76 publications

(44 citation statements)

References 58 publications

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“…Such spectra have fluorescence line widths of a few hundred reciprocal centi-narrowed (FLN) spectrometry (2,3), which affords line widths of a few reciprocal centimeters. The direct determination of substitutional PAH isomers in samples, such as solvent-refined coal, has been possible with the use of FLN spectrometry (4). This technique would be very valuable in the study of DNA adduct formation resulting from human exposure to PAH mixtures such as diesel engine emissions, cigarette smoke, or coke-oven emissions if FLN spectra [A samples isoh exposed indi-I this goal, we 12. Tebi, Cell (271982) (1981) meters, and therefore species with simicould be obtained on DN 3 .…”

mentioning

confidence: 99%

Fluorescence-Line-Narrowed Spectra of Polycyclic Aromatic Carcinogen-DNA Adducts

Heisig

Jeffrey

McGlade

et al. 1984

Science

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The laser excited fluorescence-line-narrowed spectrum of DNA modified with (+/-)-r-7,t-8-dihydroxy-t-9,10-epoxy-7,8,9,10-tetrahydrobenzo[a]pyrene (BPDE), the ultimate carcinogenic metabolite of benzo[a]pyrene (BP), has been obtained in a water-glycerol-ethanol glass at 4.2 K. The spectrum was well resolved and highly characteristic of the chromophore. Comparisons were made between the spectrum of this modified DNA and the isolated deoxyguanosine-BPDE adduct and a series of other 7,8,9,10-tetrahydro-BP (THBP) derivatives. 9-Hydroxy-BP 4,5-oxide, which is also involved in the binding of BP to DNA, and THBP have very similar conventional broadband fluorescence spectra. However, the fluorescence-line-narrowed spectra of their derivatives were readily distinguishable either as individual components or as mixtures.

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mentioning

confidence: 99%

Fluorescence-Line-Narrowed Spectra of Polycyclic Aromatic Carcinogen-DNA Adducts

Heisig

Jeffrey

McGlade

et al. 1984

Science

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“…Individual elements of our approach have been anticipated and implemented previously, including Shpol'skii studies with tunable laser excitation for site selection and selective excitation, 6 the freezing of an optical ® ber directly into the sample, 4 m ultidim ensional data form ats (e.g., excitation-emission matrices), 12±14 and the use of uorescence decays as a mathematically well-behaved way to distinguish emitting components. 11,15,16 Our goal here is simply to set the stage for a series of more detailed studies.…”

Section: Conclusio Nmentioning

confidence: 99%

“…Nor have we pushed the issue of resolution or a number of other features. For example, m ore than 15 years ago Fassel and co-workers 6 published a very nice study of tunable laser excitation of PAHs in Shpol'skii matrices. In their work the samples were ® rst frozen to 77 K and then brought to ; 15 K with a closed-cycle refrigerator.…”

Section: Conclusio Nmentioning

confidence: 99%

“…Similarly, a three-component m ixture of benzo[a]anthracene, benzo[a]pyrene, and chr ysene was separated spectroscopically. However, the authors 6 apparently stopped their work in this area about 10 years ago for reasons that are unclear (possibly the complexity of the laser excitation).…”

Section: Conclusio Nmentioning

confidence: 99%

“…Nonetheless, tunable sourcesÐ e.g., a dye laser pum ped by a pulsed nitrogen, excimer, or Nd:YAG laserÐ are advantageous for both site and analyte selection. 1,5,6 The transition wavelengths for most PAHs often require frequency doubling or mixing techniques to shift the visible laser light into the ultraviolet range. The linewidths of most Shpol'skii samples at 77 K are on the order of 20 ± 40 cm 2 1 ; even at liquid helium temperature, linewidths of less than 1 cm 2 1 are comparatively rare.…”

Section: Introductionmentioning

confidence: 99%

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Time-Resolved Laser-Excited Shpol'skii Spectrometry with a Fiber-Optic Probe and ICCD Camera

2000

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Improved methodology for chemical analysis via laser-excited Shpol'skii spectrometry is reported. The complications of traditional methodology for measurements at liquid nitrogen temperature are avoided by freezing the distal end of a bifurcated fiber-optic probe directly into the sample matrix. Emission wavelength-time matrices were rapidly collected by automatically incrementing the gate delay of an intensified charge-coupled device (ICCD) camera relative to the laser excitation pulse. The excitation source is a compact frequency-doubled tunable dye laser whose bandwidth (<0.03 nm) is well matched for Shpol'skii spectroscopy. Data reproducibility for quantitative analysis purposes and analytical figures of merit are demonstrated for several polycyclic aromatic hydrocarbons at 77 K. Although not attempted in this study, time-resolved excitation-emission matrices could easily be collected with this instrumental system.

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Resolution of complex fluorescence spectra recorded on single unpigmented living cells using a computerised method

1988

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The identification and quantification of fluorescent compounds in a complex fluorescence spectra are always difficult, especially in the case of low signaknoise ratio.We propose a computerised method that allows the resolution of low light level complex fluorescence spectra into its components.Based on a linear combination of N possible characteristic fluorescence spectra, and using N weighting functions, this method allows the integration of fluorescence intensities over the entire fluorescence spectra and the generation of n equations with N unknowns.The compounds that participate in complex fluorescence spectra are identified and quantified. Because fluorescence intensities can be integrated we can resolve complex fluorescence spectra presenting a low signaknoise ratio. The reliability and sensitivity of our method are shown through examples of resolution of complex intracellular fluorescence of single living cells pretreated with benzo(a)pyrene. Depending on the cell type and treatment, two, four, or five components can be identified in the complex fluorescence spectra.

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Laser-excited Shpol'skii spectroscopy for the selective excitation and determination of polynuclear aromatic hydrocarbons

Cited by 76 publications

References 58 publications

Fluorescence-Line-Narrowed Spectra of Polycyclic Aromatic Carcinogen-DNA Adducts

Fluorescence-Line-Narrowed Spectra of Polycyclic Aromatic Carcinogen-DNA Adducts

Time-Resolved Laser-Excited Shpol'skii Spectrometry with a Fiber-Optic Probe and ICCD Camera

Resolution of complex fluorescence spectra recorded on single unpigmented living cells using a computerised method

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