Petroleomics: Chemistry of the underworld

Abstract

Each different molecular elemental composition-e.g., CcHhNnOoSshas a different exact mass. With sufficiently high mass resolving power (m/⌬m 50% Ϸ 400,000, in which m is molecular mass and ⌬m50% is the mass spectral peak width at half-maximum peak height) and mass accuracy (<300 ppb) up to Ϸ800 Da, now routinely available from high-field (>9.4 T) Fourier transform ion cyclotron resonance mass spectrometry, it is possible to resolve and identify uniquely and simultaneously each of the thousands of elemental compositions from the most complex natural organic mixtures, including petroleum crude oil. It is thus possible to separate and sort petroleum components according to their heteroatom class (N nOoSs), double bond equivalents (DBE ‫؍‬ number of rings plus double bonds involving carbon, because each ring or double bond results in a loss of two hydrogen atoms), and carbon number. ''Petroleomics'' is the characterization of petroleum at the molecular level. From sufficiently complete characterization of the organic composition of petroleum and its products, it should be possible to correlate (and ultimately predict) their properties and behavior. Examples include molecular mass distribution, distillation profile, characterization of specific fractions without prior extraction or wet chemical separation from the original bulk material, biodegradation, maturity, water solubility (and oil:water emulsion behavior), deposits in oil wells and refineries, efficiency and specificity of catalytic hydroprocessing, ''heavy ends'' (asphaltenes) analysis, corrosion, etc.Fourier transform ͉ ion cyclotron resonance ͉ mass spectrometry ͉ petroleum ͉ fossil fuel

Formation of nitrogenated organic aerosols in the Titan upper atmosphere

“…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).…”

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

“…[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.…”

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

“…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].…”