Publications by authors named "Melissa Dunkle"

In steam cracking, upstream pyrolysis oil hydroprocessing, and in many downstream processes, olefinic content is key to assess process performance and process safety risk associated with highly exothermic reactions. When looking to plastic pyrolysis oils as a potential feedstock, as well as downstream products such as pyrolysis gasoline (pygas), these materials contain unsaturated hydrocarbons which are not present in fossil feedstocks. Pygas is a product of pyrolysis and exhibits a large number of chemical structural similarities with plastic pyrolysis oils, especially in terms of olefins structure.

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Comprehensive two-dimensional liquid chromatography (LC × LC) is an attractive separation technique that allows achieving high peak capacities and information on chemical correlations. Unfortunately, its application in industrial practice is still not widespread due to limiting factors such as complex method development, tedious method optimization and solvent-incompatibility (such as solvent-strength mismatch or immiscibility experienced during fraction transfer). A severe case of solvent-incompatibility is encountered in the comprehensive coupling of normal-phase LC and reversed-phase LC (NPLC × RPLC).

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Understanding the relation between chemical characteristics and properties of synthetic polymers is one of the challenges faced by analytical chemists in industry. This is a complex task, as polymers are not synthesized as single molecule, but are populations of chemically similar compounds with distributions over several properties. The latter include, for example, molecular weight, nature of end-groups (functionality), and chemical composition.

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The conversion of waste streams into a useable material through a recycling process is a hot topic. Waste streams can originate from domestic and industrial sources and range from plastic waste to medical waste to various industrial waste streams, both solid and liquid. In addition to waste circularity, circularity for bio-based waste streams and renewable sources are also being investigated.

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Hydrocarbons analysis is important in the oil and gas industry, as stream composition has a strong impact on plant operations. The composition of hydrocarbon streams vary across a plant, which makes the selection of analytical methods challenging. Traditional methods for the evaluation of liquid hydrocarbon streams include the Detailed Hydrocarbon Analysis (DHA); however, non-traditional methods, such as comprehensive gas chromatography (GCxGC), are also utilized in the chemical industry, including Dow.

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Polyether polyols are often used in formulated systems, but their complete characterization is challenging, because of simultaneous heterogeneities in chemical composition, molecular weight and functionality. One-dimensional liquid chromatography-mass spectrometry is commonly used to characterize polyether polyols. However, the separation power of this technique is not sufficient to resolve the complexity of such samples entirely.

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Electrospray ionization (ESI) of solution mixtures often generates complex mass spectra, even following liquid chromatography (LC), due to analyte multiple charging. Multiple charge state distributions can lead to isobaric interferences, mass spectral congestion, and ambiguous ion identification. As a consequence, data interpretation increases in complexity.

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Detailed lipidomics experiments were performed on the extracts of cured tobacco leaf and of cigarette smoke condensate (CSC) using high-resolution liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (LC-Q-TOF MS). Following automated solid-phase extraction (SPE) fractionation of the lipid extracts, over 350 lipids could be annotated. From a large-scale study on 22 different leaf samples, it was determined that differentiation based on curing type was possible for both the tobacco leaf and the CSC extracts.

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The absolute configuration of rhizopine, an opine-like natural product present in nitrogen-fixing nodules of alfalfa infected by rhizobia, is elucidated using a combination of state-of-the-art analytical and semi-preparative supercritical fluid chromatography and vibrational circular dichroism spectroscopy. A synthetic peracetylated racemate was fractionated into its enantiomers and subjected to absolute configuration analysis revealing that natural rhizopine exists as a single enantiomer. The stereochemistry of non-derivatized natural rhizopine corresponds to (1R,2S,3R,4R,5S,6R)-4-amino-6-methoxycyclohexane-1,2,3,5-tetraol.

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