A variety of organic compounds in human exhaled breath were measured online by mass spectrometry using the fifth (206 nm) and fourth (257 nm) harmonic emissions of a femtosecond ytterbium (Yb) laser ...as the ionization source. Molecular ions were enhanced significantly by means of resonance-enhanced, two-color, two-photon ionization, which was useful for discrimination of analytes against the background. The limit of detection was 0.15 ppm for acetone in air. The concentration of acetone in exhaled breath was determined for three subjects to average 0.31 ppm, which lies within the range of normal healthy subjects and is appreciably lower than the range for patients with diabetes mellitus. Many other constituents, which could be assigned to acetaldehyde, ethanol, isoprene, phenol, octane, ethyl butanoate, indole, octanol, etc., were observed in the exhaled air. Therefore, the present approach shows potential for use in the online analysis of diabetes mellitus and also for the diagnosis of various diseases, such as COVID-19 and cancers.A variety of organic compounds in human exhaled breath were measured online by mass spectrometry using the fifth (206 nm) and fourth (257 nm) harmonic emissions of a femtosecond ytterbium (Yb) laser as the ionization source. Molecular ions were enhanced significantly by means of resonance-enhanced, two-color, two-photon ionization, which was useful for discrimination of analytes against the background. The limit of detection was 0.15 ppm for acetone in air. The concentration of acetone in exhaled breath was determined for three subjects to average 0.31 ppm, which lies within the range of normal healthy subjects and is appreciably lower than the range for patients with diabetes mellitus. Many other constituents, which could be assigned to acetaldehyde, ethanol, isoprene, phenol, octane, ethyl butanoate, indole, octanol, etc., were observed in the exhaled air. Therefore, the present approach shows potential for use in the online analysis of diabetes mellitus and also for the diagnosis of various diseases, such as COVID-19 and cancers.
A sample mixture of fatty acid methyl esters (FAMEs) was measured by femtosecond laser ionization mass spectrometry (fsLIMS) using the fifth (206 nm) and fourth (257 nm) harmonic emissions of an ...ytterbium (Yb) laser (1030 nm). Molecular ions were observed as the major signals in this technique, providing valuable information concerning the molecular weight and the number of double bonds in the molecule. The mass spectral data were then used as explanatory variables in machine learning based on artificial intelligence (AI) to correlate with objective variables such as the cetane number, kinematic viscosity, specific gravity, a higher heating value, an iodine value, flash point, oxidative stability index, and a cloud point measured for reference biofuel samples containing various FAMEs. The properties of biofuels, i.e., the objective variables, were evaluated from the mass spectral data obtained for unknown samples. The errors in the evaluation were a few percent when the distribution of the FAMEs in the unknown biofuel sample was similar to those of the biofuels used for machine learning. As demonstrated herein, the present approach, involving a combination of fsLIMS and AI, has the potential for use in evaluating the properties of a biofuel and then in solving of environmental issues associated with global warming.
A standard sample mixture containing thirty-seven fatty acid methyl esters (FAMEs) was measured by femtosecond laser ionization mass spectrometry. FAME molecules with double bonds were efficiently ...ionized via resonance-enhanced two-photon ionization by absorbing the first photon at 206 nm at the edge of the absorption band of the π→π* transition and subsequently ionized by absorbing the second photon at 257 nm. The intensity of the molecular radical ion was enhanced significantly using this two-color ionization scheme, which minimizes the excess energy in the ionized state, when compared with electron ionization mass spectrometry and vacuum-ultraviolet photoionization mass spectrometry. This approach was then used for the reliable identification of FAMEs contained in an actual sample of biofuel.
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•Fatty acid methyl esters (FAMEs) were measured by mass spectrometry.•FAMEs were ionized using a femtosecond laser as the ionization source (fsLIMS).•FAMEs were ionized using a two-color two-photon ionization scheme at 206/257 nm.•The signal intensity of a molecular radical ion was enhanced for unsaturated FAMEs.•FAMEs contained in a real sample of biofuel was determined using this technique.
The spectral domain of an ultraviolet femtosecond laser was expanded by stimulated Raman scattering/four-wave Raman mixing, and the resulting laser pulse was compressed using a pair of gratings. The ...pulse width was then measured using an autocorrelator comprised of a Michelson interferometer equipped with a multiphoton ionization/mass spectrometer which was used as a two-photon detector. A gas chromatograph/mass spectrometer was employed to analyze triacetone triperoxide (TATP), and the molecular ion induced by multiphoton ionization was substantially enhanced by decreasing the laser pulse width.
Gas chromatography/multiphoton ionization/time-of-flight mass spectrometry (GC/MPI/TOF-MS) was applied to the trace analysis of polychlorinated dibenzo-
p-dioxins and polychlorinated dibenzofurans ...(PCDD/Fs). To determine the optimum wavelength for analysis of PCDD/Fs, the wavelength of the femtosecond laser utilized for multiphoton ionization was converted to near-ultraviolet status using stimulated Raman scattering. A femtosecond laser emitting at 300
nm completely eliminated the background signal arising from the bleeding compounds generated from a stationary phase of the capillary column in GC.
A simple method was proposed for on-site evaluation of the pulse width of an ultraviolet femtosecond laser coupled with a mass spectrometer. This technique was based on measurement of a two-photon ...ionization signal in mass spectrometry by translation of the prism in the pulse compressor of the femtosecond laser. The method was applied to optical pulses that were emitted at wavelengths of 267, 241, and 219 nm; the latter two pulses were generated by four-wave Raman mixing using the third harmonic emission of a Ti:sapphire laser (267 nm) in hydrogen gas. The measurement results show that this approach is useful for evaluation of the pulse width of the ultraviolet femtosecond laser used in mass spectrometry for trace analysis of organic compounds.
Barbiturates are highly susceptible to dissociation in mass spectrometry (MS) because of their long side chains combined with a nonaromatic ring consisting of several carbonyl and amine groups. As a ...result, they exhibit extensive α-cleavage and subsequent rearrangement, making the identification of these compounds difficult. Although a library of electron ionization MS (EIMS) is available, most barbiturates have very similar fragment patterns. Accordingly, it would be desirable to develop a technique for soft ionization, providing a molecular ion and large fragment ions as well. In this study, a molecular ion was clearly observed, in addition to large fragment ions, for a variety of barbiturates based on multiphoton ionization MS (MPIMS) using a tunable ultraviolet femtosecond laser as the ionization source (fs-LIMS). This favorable result was achieved when the optimal laser wavelength for minimizing the excess energy remaining in the ionic state was used. An examination of the photofragmentation pathways suggested that an H atom in the side chain was abstracted by an oxygen atom in the carbonyl group in the ring structure thus initiating fragmentation and subsequent rearrangement. Barbiturates that are substituted with alkyl groups (amobarbital and pentobarbital) had narrower spectral regions for optimal ionization than the other barbiturates with alkyl and alkenyl groups (butalbital and secobarbital) and more with alkyl and phenyl groups (phenobarbital). All of the barbiturates studied provided unique mass spectral patterns in fs-LIMS, which was useful for the reliable identification of these compounds in practical trace analysis.
•Femtosecond ionization mass spectrometry is combined with gas chromatography.•A molecular ion can be enhanced in femtosecond ionization mass spectrometry.•An aliphatic compound can be efficiently ...ionized via nonresonant two-photon process.•A variety of organic compounds such as pesticides and explosives have been measured.•Two-dimensional GC-MS display can be successfully used for comprehensive analysis.
Mass spectrometry is now in widespread use for the detection of the analytes separated by chromatography. Electron ionization is the most frequently used method in mass spectrometry. However, this ionization technique sometimes suffers from extensive fragmentation of analytes, which makes identification difficult. A photoionization technique has been developed for suppressing this fragmentation and for subsequently observing a molecular ion. A variety of lasers have been employed for the sensitive and selective ionization of organic compounds. A femtosecond laser has a high peak power and is preferential for efficient ionization as well as for suppressing fragmentation, providing valuable information concerning molecular weight and chemical structure as well. In this review, we report on applications of femtosecond ionization mass spectrometry combined with gas chromatography.
The frequency domain of non-resonant two-photon ionization, defined as a frequency separation from half of the ionization energy to the excitation energy, was investigated using density functional ...theory calculations. Several organic compounds have the potential for use in the measurement of the ultrashort optical pulse width in the ultraviolet region using an autocorrelator consisting of a mass spectrometer as a two-photon-response detector.
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