Petroleomics: Chemistry of the underworld

Marshall, Alan G.; Rodgers, Ryan P.

doi:10.1073/pnas.0805069105

Cited by 620 publications

(591 citation statements)

References 57 publications

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“…In order to investigate the functional diversity and the possible precursors, all identified ion species are plotted with the aid of van Krevelen diagrams (25,26) (Fig. 5A).…”

Section: Resultsmentioning

confidence: 99%

Formation of nitrogenated organic aerosols in the Titan upper atmosphere

Imanaka

Smith

2010

Proc. Natl. Acad. Sci. U.S.A.

107

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Many aspects of the nitrogen fixation process by photochemistry in the Titan atmosphere are not fully understood. The recent Cassini mission revealed organic aerosol formation in the upper atmosphere of Titan. It is not clear, however, how much and by what mechanism nitrogen is incorporated in Titan's organic aerosols. Using tunable synchrotron radiation at the Advanced Light Source, we demonstrate the first evidence of nitrogenated organic aerosol production by extreme ultraviolet-vacuum ultraviolet irradiation of a N 2 ∕CH 4 gas mixture. The ultrahigh-mass-resolution study with laser desorption ionization-Fourier transform-ion cyclotron resonance mass spectrometry of N 2 ∕CH 4 photolytic solid products at 60 and 82.5 nm indicates the predominance of highly nitrogenated compounds. The distinct nitrogen incorporations at the elemental abundances of H 2 C 2 N and HCN, respectively, are suggestive of important roles of H 2 C 2 N∕HCCN and HCN∕CN in their formation. The efficient formation of unsaturated hydrocarbons is observed in the gas phase without abundant nitrogenated neutrals at 60 nm, and this is confirmed by separately using 13 C and 15 N isotopically labeled initial gas mixtures. These observations strongly suggest a heterogeneous incorporation mechanism via short lived nitrogenated reactive species, such as HCCN radical, for nitrogenated organic aerosol formation, and imply that substantial amounts of nitrogen is fixed as organic macromolecular aerosols in Titan's atmosphere.

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“…In order to investigate the functional diversity and the possible precursors, all identified ion species are plotted with the aid of van Krevelen diagrams (25,26) (Fig. 5A).…”

Section: Resultsmentioning

confidence: 99%

Formation of nitrogenated organic aerosols in the Titan upper atmosphere

Imanaka

Smith

2010

Proc. Natl. Acad. Sci. U.S.A.

107

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“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] From a fundamental point of view, tetrazoles are also particularly interesting systems, especially because of the tautomerism they may exhibit and their diversified photochemistry. 1,[21][22][23][24][25][26][27][28][29] Unsubstituted tetrazole, for example, was found to exist exclusively in the crystalline phases as the 1H-tautomer, [30][31][32] whereas in solution and gas phase 1H-and 2H-tautomers coexist, the population of the most polar 1H form increasing with the polarity of the solvent.…”

Section: Introductionmentioning

confidence: 99%

Tautomer Selective Photochemistry in 1-(Tetrazol-5-yl)ethanol

et al. 2010

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A combined matrix isolation FTIR and theoretical DFT/B3LYP/6-311++G(d,p) study of the molecular structure and photochemistry of 1-(tetrazol-5-yl)ethanol [1-TE] was performed. The potential energy surface landscapes of the 1H and 2H tautomers of the compound were investigated and the theoretical results were used to help characterize the conformational mixture existing in equilibrium in the gas phase prior to deposition of the matrices, as well as the conformers trapped in the latter. In the gas phase, at room temperature, the compound exists as a mixture of 12 conformers (five of the 1H tautomer and seven of the 2H tautomer). Upon deposition of the compound in an argon matrix at 10 K, only three main forms survive, because the low barriers for conformational isomerization allow extensive conformational cooling during deposition. Deposition of the matrix at 30 K led to further simplification of the conformational mixture with only one conformer of each tautomer of 1-TE surviving. These conformers correspond to the most stable forms of each tautomer, which bear different types of intramolecular H-bonds: 1H-I has an NH · · · O hydrogen bond, whereas 2H-I has an OH · · · N hydrogen bond. Upon irradiating with UV light (λ > 200 nm), a matrix containing both 1H-I and 2H-I forms, an unprecedented tautomer selective photochemistry was observed, with the 2H tautomeric form undergoing unimolecular decomposition to azide + hydroxypropanenitrile and the 1H-tautomer being photostable.

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“…Unfortunately, the mass spectrometric characterization of hydrocarbons and their mixtures, such as biofuels, is challenging due to the shortcomings of current ionization methods. For example, ESI [12], SSI [10,11], and matrix-assisted laser desorption/ionization [13] (MALDI) are limited to ionization via protonation, deprotonation, and cation attachment [14,15], which means that these methods cannot ionize analytes without easily ionizable functional groups, such as saturated hydrocarbons [16,18]. Ambient analysis of saturated hydrocarbons by using dischargeinduced oxidation in desorption electrospray ionization (DESI) has been reported [19].…”

Section: Introductionmentioning

confidence: 99%

HPLC/APCI Mass Spectrometry of Saturated and Unsaturated Hydrocarbons by Using Hydrocarbon Solvents as the APCI Reagent and HPLC Mobile Phase

Gao

Owen

Borton

et al. 2012

J. Am. Soc. Mass Spectrom.

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Saturated and unsaturated, linear, branched, and cyclic hydrocarbons, as well as polyaromatic and heteroaromatic hydrocarbons, were successfully ionized by atmospheric pressure chemical ionization (APCI) using small hydrocarbons as reagents in a linear quadrupole ion trap (LQIT) mass spectrometer. Pentane was proved to be the best reagent among the hydrocarbon reagents studied. This ionization method generated different types of abundant ions (i.e., [M + H] , with little or no fragmentation. The radical cations can be differentiated from the even-electron ions by using dimethyl disulfide, thus facilitating molecular weight (MW) determination. While some steroids and lignin monomer model compounds, such as androsterone and 4-hydroxy-3-methoxybenzaldehyde, also formed abundant M +• and [M+H] + ions, this was not true for all of them. Analysis of two known mixtures as well as a base oil sample demonstrated that each component of the known mixtures could be observed and that a correct MW distribution was obtained for the base oil. The feasibility of using this ionization method on the chromatographic time scale was demonstrated by using high-performance liquid chromatography (HPLC) with hexane as the mobile phase (and APCI reagent) to separate an artificial mixture prior to mass spectrometric analysis.

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Petroleomics: Chemistry of the underworld

Cited by 620 publications

References 57 publications

Formation of nitrogenated organic aerosols in the Titan upper atmosphere

Formation of nitrogenated organic aerosols in the Titan upper atmosphere

Tautomer Selective Photochemistry in 1-(Tetrazol-5-yl)ethanol

HPLC/APCI Mass Spectrometry of Saturated and Unsaturated Hydrocarbons by Using Hydrocarbon Solvents as the APCI Reagent and HPLC Mobile Phase

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