Chemical compositional analysis of jet fuels: Contributions of mass spectrometry in the 21st century.

Jet fuels are complex mixtures composed of many individual compounds that influence crucial chemical and physical properties. Approximately over the last 20 years, mass spectrometry studies provided important and extensive qualitative and quantitative information of the compounds that make up jet fuels. This review presents these main findings, evaluates the analytical methods utilized, and summarizes the hydrocarbons, nitrogen-, oxygen- and sulfur-containing compounds characterized in the jet fuels. Potential areas where mass spectrometry may play important roles in the future will also be discussed.

Polyphenols bind to low density lipoprotein at biologically relevant concentrations that are protective for heart disease.

There is ample evidence in the epidemiological literature that polyphenols, the major non-vitamin antioxidants in plant foods and beverages, have a beneficial effect on heart disease. Until recently other mechanisms which polyphenols exhibit such as cell signaling and regulating nitric oxide bioavailability have been investigated. The oxidation theory of atherosclerosis implicates LDL oxidation as the beginning step in this process. Nine polyphenols from eight different classes and several of their O-methylether, O-glucuronide and O-sulfate metabolites have been shown in this study to bind to the lipoproteins and protect them from oxidation at lysosomal/inflammatory pH (5.2), and physiological pH (7.4). Polyphenols bind to the apoprotein at pH 7.4 with Kb > 106 M-1 and the number of molecules of polyphenols bound per LDL particle under saturation conditions varied from 0.4 for ferulic acid to 13.1 for quercetin. Competition studies between serum albumin and LDL show that substantial lipoprotein binding occurs even in the presence of a great molar excess of albumin, the major blood protein. These in vitro results are borne out by published human supplementation studies showing that polyphenol metabolites from red wine, olive oil and coffee are found in LDL even after an overnight fast. A single human supplementation with various fruit juices, coffee and tea also produced an ex vivo protection against lipoprotein oxidation under postprandial conditions. This in vivo binding is heart-protective based on published olive oil consumption studies. Relevant to heart disease, we hypothesize that the binding of polyphenols and metabolites to LDL functions as a transport mechanism to carry these antioxidants to the arterial intima, and into endothelial cells and macrophages. Extracellular and intracellular polyphenols and their metabolites are heart-protective by many mechanisms and can also function as potent "intraparticle" and intracellular antioxidants due to their localized concentrations that can reach as high as the micromolar level. Low plasma concentrations make polyphenols and their metabolites poor plasma antioxidants but their concentration in particles such as lipoproteins and cells is high enough for polyphenols to provide cardiovascular protection by direct antioxidant effects and by other mechanisms such as cell signaling.

Distinguishing Isomeric Aromatic Radical Cations by Using Energy-Resolved Ion Trap and Medium Energy Collision-Activated Dissociation Mass Spectrometry.

Different collision-activated dissociation (CAD) methods were evaluated for their effectiveness at distinguishing several ionized isomeric aromatic compounds by using a linear quadrupole ion trap/orbitrap mass spectrometer. The compounds were ionized by using atmospheric pressure chemical ionization (APCI) with carbon disulfide solvent in the positive ion mode to generate stable molecular ions with limited fragmentation. They were subjected to CAD in the linear quadrupole ion trap (ITCAD) and in an octupole collision cell (medium-energy collision-activated dissociation, MCAD; also known as HCD). Experiments conducted by attempting to vary ion activation times revealed that MCAD and ITCAD occur in the microsecond and millisecond time regimes, respectively. MCAD was found to impart substantially greater internal energies into the molecular ions compared to ITCAD. Accordingly, molecular ions subjected to MCAD favored dissociation via fast σ-bond cleavages, while molecular ions subjected to ITCAD tended to favor rearrangement reactions. MCAD used in the energy-resolved mode (ER-MCAD) enabled the distinction of six ionized isomeric compounds from each other based on modified crossing-point energies (collision energies where the molecular ions and selected fragment ions have an equal abundance). This was not true for ER-ITCAD. Overall, MCAD was superior over ITCAD at the differentiation of isomeric ions, and it provided more detailed structural information.

Nitrogen Compound Characterization in Fuels by Multidimensional Gas Chromatography.

Certain nitrogen-containing compounds can contribute to fuel instability during storage. Hence, detection and characterization of these compounds is crucial. There are significant challenges to overcome when measuring trace compounds in a complex matrix such as fuels. Background interferences and matrix effects can create limitations to routine analytical instrumentation, such as GC-MS. In order to facilitate specific and quantitative measurements of trace nitrogen compounds in fuels, a nitrogen-specific detector is ideal. In this method, a nitrogen chemiluminescence detector (NCD) is used to detect nitrogen compounds in fuels. NCD utilizes a nitrogen-specific reaction that does not involve the hydrocarbon background. Two-dimensional (GCxGC) gas chromatography is a powerful characterization technique as it provides superior separation capabilities to one-dimensional gas chromatography methods. When GCxGC is paired with a NCD, the problematic nitrogen compounds found in fuels can be extensively characterized without background interference. The method presented in this manuscript details the process for measuring different nitrogen-containing compound classes in fuels with little sample preparation. Overall, this GCxGC-NCD method has been shown to be a valuable tool to enhance the understanding of the chemical composition of nitrogen-containing compounds in fuels and their impact on fuel stability. The % RSD for this method is <5% for intraday and <10% for interday analyses; the LOD is 1.7 ppm and the LOQ is 5.5 ppm.

Identification and Quantitation of Linear Alkanes in Lubricant Base Oils by Using GC×GC/EI TOF Mass Spectrometry.

Linear alkanes are a class of compounds known to negatively affect the physical performance of lubricant base oils. The ability to rapidly identify and quantify linear alkanes in lubricant base oils would enable oil companies to more effectively evaluate their refinery methods for converting crude oil to lubricant base oils. While mass spectrometry is a powerful method for elucidation of the structures of compounds in complex mixtures, it is not innately quantitative. An approach is presented here for the identification and quantitation of linear alkanes in base oil samples by utilizing GC×GC/EI TOF MS. Identification of the linear alkanes in base oils was achieved based on their retention times in both GC columns as well as their EI mass spectra. Linear alkane model compound mixtures were used to generate calibration plots for quantitation of the linear alkanes in the base oils. The accuracy of this method was greater than 83.8%, within-day precision lower than 6.2%, between-day precision lower than 16.2%, and total precision lower than 17.2%. All noted figures of merit surpass the acceptable limits for a new validated quantitative method, where accuracy must be better than 80% and precision lower than 20% at the lower limit of quantitation. The n-alkane content in both base oil samples was further validated using a GC×GC/FID method (the gold standard for quantitation), which provided nearly identical results to those obtained using the GC×GC/EI TOF MS method. Therefore, GC×GC/EI TOF MS can be used to both identify and quantitate linear alkanes.

Comparison of Atmospheric Pressure Chemical Ionization and Field Ionization Mass Spectrometry for the Analysis of Large Saturated Hydrocarbons.

Direct infusion atmospheric pressure chemical ionization mass spectrometry (APCI-MS) was compared to field ionization mass spectrometry (FI-MS) for the determination of hydrocarbon class distributions in lubricant base oils. When positive ion mode APCI with oxygen as the ion source gas was employed to ionize saturated hydrocarbon model compounds (M) in hexane, only stable [M - H]+ ions were produced. Ion-molecule reaction studies performed in a linear quadrupole ion trap suggested that fragment ions of ionized hexane can ionize saturated hydrocarbons via hydride abstraction with minimal fragmentation. Hence, APCI-MS shows potential as an alternative of FI-MS in lubricant base oil analysis. Indeed, the APCI-MS method gave similar average molecular weights and hydrocarbon class distributions as FI-MS for three lubricant base oils. However, the reproducibility of APCI-MS method was found to be substantially better than for FI-MS. The paraffinic content determined using the APCI-MS and FI-MS methods for the base oils was similar. The average number of carbons in paraffinic chains followed the same increasing trend from low viscosity to high viscosity base oils for the two methods.