Evaluation of Ultrahigh-Performance Supercritical Fluid Chromatography–Mass Spectrometry as an Alternative Approach for the Analysis of Fatty Acid Methyl Esters in Aviation Turbine Fuel

Bio-oils are precursors for biofuels but are highly corrosive necessitating further upgrading. Furthermore, bio-oil samples are highly complex and represent a broad range of chemistries. They are complex mixtures not simply because of the large number of poly-oxygenated compounds but because each composition can comprise many isomers with multiple functional groups. The use of hyphenated ultrahigh-resolution mass spectrometry affords the ability to separate isomeric species of complex mixtures. Here, we present for the first time, the use of this powerful analytical technique combined with chemical reactivity to gain greater insights into the reactivity of the individual isomeric species of bio-oils. A pyrolysis bio-oils and its esterified bio-oil were analyzed using gas chromatography coupled to Fourier transform ion cyclotron resonance mass spectrometry, and in-house software (KairosMS) was used for fast comparison of the hyphenated data sets. The data revealed a total of 10,368 isomers in the pyrolysis bio-oil and an increase to 18,827 isomers after esterification conditions. Furthermore, the comparison of the isomeric distribution before and after esterification provide new light on the reactivities within these complex mixtures; these reactivities would be expected to correspond with carboxylic acid, aldehyde, and ketone functional groups. Using this approach, it was possible to reveal the increased chemical complexity of bio-oils after upgrading and target detection of valuable compounds within the bio-oils. The combination of chemical reactions alongside with in-depth molecular characterization opens a new window for the understanding of the chemistry and reactivity of complex mixtures.

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“…An alternative separation method to GC to study high-molecular-weight components in bio-oils may be SFC. 14 , 38 …”

Section: Resultsmentioning

confidence: 99%

Revealing the Reactivity of Individual Chemical Entities in Complex Mixtures: the Chemistry Behind Bio-Oil Upgrading

et al. 2022

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“…This make‐up solvent can also be used to produce specific ions, e.g. the addition of sodium ions to the make‐up flow to produce sodiated molecules, thus ensuring optimum sensitivity for quantitative analysis . In an open access environment, additional column ovens, with a range of six column phases, and four co‐solvent channels provide optimal flexibility.…”

Section: University Of Southampton Chemistry Mass Spectrometrymentioning

confidence: 99%

Open Access UHPSFC/MS – an additional analytical resource for an academic mass spectrometry facility

Herniman

Langley

2016

Rapid Comm Mass Spectrometry

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RATIONALE:Many compounds submitted for analysis in Chemistry at the University of Southampton do not retain, elute or ionize using open access reversed-phase ultra-high-performance liquid chromatography/mass spectrometry (RP-UHPLC/MS) and require analysis via infusion. An ultra-high-performance supercritical fluid chromatography mass spectrometry approach was implemented to afford high-throughput analysis of these compounds with chromatographic separation. METHODS: A UPC 2 -TQD MS system has been incorporated into the open access MS provision within Chemistry at the University of Southampton, using an ESCi source (electrospray and atmospheric pressure chemical ionization) and an atmospheric pressure photoionization (APPI) source. Access to instrumentation is enabled via a web-based interface (RemoteAnalyzer ™ ). RESULTS: Compounds such as fluorosugars, fullerenes, phosphoramidites, porphyrins, and rotaxanes exhibiting properties incompatible with RP-UHPLC/MS have been analyzed using automated chromatography and mass spectrometry methods. The speedy return of data enables research in these areas to progress unhindered by sample type. The provision of an electronic web format enables easy incorporation of chromatograms and mass spectra into electronic files and reports. CONCLUSIONS: The implementation of UHPSFC/MS increases access to a wide range of chemistries incompatible with reversed-phase chromatography and polar solvents, enabling more than 90% of submitted samples to be analyzed using an open access approach. Further, chromatographic separation is provided where previously flow injection or infusion analyses were the only options.

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“…Polar organic co-solvents (modifiers) are often used in conjunction with scCO 2 in order to extend the breadth of compounds accessible to UHPSFC by increasing the polarity of the mobile phase. Methanol is the most common co-solvent often enhanced by the addition of additives such as ammonium acetate, ammonium formate, or formic acid [23].…”

Section: Introductionmentioning

confidence: 99%

Development of ultra‐high‐performance supercritical fluid chromatography‐mass spectrometry assays to analyze potential biomarkers in sweat

Herniman

Worsley

Greenhill

et al. 2021

J of Separation Science

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Liquid chromatography-mass spectrometry methods were required to afford the rapid separation and detection of purines and small organic acids. These compounds are found in sweat and sebum and are potential biomarkers for the early detection of pressures sores. Two ultra-high-performance supercritical fluid chromatography-mass spectrometry assays have been successfully developed for both classes of compounds. Separation for purines was achieved using a gradient of supercritical carbon dioxide and methanol with a 1-aminoanthracene sub 2 μm particle size column followed by positive ion electrospray ionization. Separation for organic acids was achieved using a gradient of supercritical carbon dioxide and methanol (50 mM ammonium acetate 2% water) with a Diol sub 2 μm particle size column followed by negative ion electrospray ionization. Calibration curves were created in the absence of internal standards and R 2 values > 0.96 were achieved using single ion monitoring methods for the protonated purines and the deprotonated acids. The two new assays afford rapid analytical methods for the separation and detection of potential biomarkers in human sweat leading to the early detection and prevention of pressure sores.

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Evaluation of Ultrahigh-Performance Supercritical Fluid Chromatography–Mass Spectrometry as an Alternative Approach for the Analysis of Fatty Acid Methyl Esters in Aviation Turbine Fuel

Cited by 12 publications

References 20 publications

Revealing the Reactivity of Individual Chemical Entities in Complex Mixtures: the Chemistry Behind Bio-Oil Upgrading

Revealing the Reactivity of Individual Chemical Entities in Complex Mixtures: the Chemistry Behind Bio-Oil Upgrading

Open Access UHPSFC/MS – an additional analytical resource for an academic mass spectrometry facility

Development of ultra‐high‐performance supercritical fluid chromatography‐mass spectrometry assays to analyze potential biomarkers in sweat

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