Fragmentation-fluorescence spectrometric determination of nonfluorescent compounds

E. L. Wehry; Ronald Hohmann; Jane K. Gates; Lauralee F. Guilbault; Priscilla M. Johnson; John S. Schendel; David A. Radspinner

doi:10.1364/AO.26.003559

Applied Optics
Vol. 26,
Issue 17,
pp. 3559-3565
(1987)
•https://doi.org/10.1364/AO.26.003559

Fragmentation-fluorescence spectrometric determination of nonfluorescent compounds

E. L. Wehry, Ronald Hohmann, Jane K. Gates, Lauralee F. Guilbault, Priscilla M. Johnson, John S. Schendel, and David A. Radspinner

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E. L. Wehry, Ronald Hohmann, Jane K. Gates, Lauralee F. Guilbault, Priscilla M. Johnson, John S. Schendel, and David A. Radspinner, "Fragmentation-fluorescence spectrometric determination of nonfluorescent compounds," Appl. Opt. 26, 3559-3565 (1987)

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Abstract

The use of molecular fragmentation for fluorometric detection and quantification of nonfluorescent organic and organometallic compounds is described. The measurements are based on the emissive characteristics of many small molecular fragments (OH, CN, CH, etc.). Fragmentation is induced by 100-eV electrons or 193-nm photons. Limits of detection, linearity, reproducibility, and range of applicability of the measurements are discussed. The merits of laser photolysis and electron impact as techniques for generating fluorescent fragments from nonfluorescent analyte molecules are compared.

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Compounds	Fragment/Transition	Limit of Detection^a	Linear Dynamic Range^a	Precision^b (%)
N₂	${N_{2}}^{+} (B^{2} \sum_{u}^{+} \to X^{2} \sum_{g}^{+})$ , 391.9 nm	5 × 10⁻⁸	1 × 10⁻⁷−9 × 10⁻⁴	1.0
CH₃NO₂	CH(A²Δ → X²Π), 431.4 nm	5 × 10⁻⁷	8 × 10⁻⁶−8 × 10⁻⁴	0.77
1-Nitropropane	H_β, 486.1 nm	7 × 10⁻⁷	—	0.95
2-Nitropropane	H_β, 486.1 nm	1 × 10⁻⁶	5 × 10⁻⁶−5 × 10⁻⁴	1.2
CH₃CN	CN(B²Σ⁺ → X²Σ⁺), 388.3 nm	6 × 10⁻⁷	1 × 10⁻⁶−3 × 10⁻⁴	2.0
NH₃	NH(A³Π → X³Σ), 336.0 nm	1 × 10⁻⁷	4 × 10⁻⁷−8 × 10⁻⁴	1.4
CH₃NH₂	H_β, 486.1 nm	1.5 × 10⁻⁶	8 × 10⁻⁷−2 × 10⁻⁴	1.2
CH₂CI₂	H_β, 486.1 nm	6 × 10⁻⁷	—	1.0

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Applied Optics