Author ORCID Identifier
Date Available
8-15-2022
Year of Publication
2022
Degree Name
Doctor of Philosophy (PhD)
Document Type
Doctoral Dissertation
College
Arts and Sciences
Department/School/Program
Chemistry
First Advisor
Dr. Bert C. Lynn
Abstract
Plant-derived compounds have the potential to produce value-added compounds with a variety of applications. For example, the lignin part of the lignocellulosic biomass, produced in large quantities as waste from the paper and pulp industries, is a rich source of phenolics with potential applications in the renewable energy sector, pharmaceutical, and chemical industries. On the other hand, plant alkaloids are the primary source for developing plant-derived therapeutics. Unfortunately, the recalcitrant nature of plant cell walls, low extraction yields of small secondary metabolites, and the lack of effective analytical methods for a rapid and accurate identification of plant-based compounds and plant’s degradation products are the major limitations in plant-based valorization efforts.
In order to address some of these challenges, this dissertation focuses on utilizing different mass spectrometry-based techniques such as UHPLC-MS, GC-MS, and direct infusion high-resolution accurate orbitrap and ion trap mass spectrometry for the detection and structure elucidation of plant-based phenolics and alkaloids in order to contribute to ongoing efforts toward valorization of plant-based compounds. Mass spectrometry-based techniques are widely used in pharmaceutical and chemical industries, and have been emerged as one of the most promising analytical techniques for the analysis of plant-based compounds.
The main aim of this dissertation is to develop effective mass spectrometry-based techniques to characterize plant-based phenolics and alkaloids. In order to do so, in the second chapter of this dissertation, a mass spectrometric method based on lithium cationization was developed to sequence lignin model oligomers with mixed bonding motifs, with a potential application in facilitating the structure elucidation of lignin degradation end products with β-β and β-O-4 linkages. In the third chapter, using UHPLC-MS, an important lignan, syringaresinol, was characterized in bourbon whiskey. The origin of syringaresinol was investigated using a model aging experiment to further our understanding of bourbon’s chemical composition. In chapter four, the development of a mild ethanosolv treatment combined with a GC-MS method enabled the detection of several different phenolic compounds in lignocellulosic biomass, which can be potentially used to rapidly compare different biomass samples for the valorization applications. Lastly, in chapter five, synthetic methods in combination with extensive mass spectrometry-based analysis were used to semi-synthesize new plant-based alkaloids with potential applications in drug discovery and development.
Overall, these studies confirm that mass spectrometry-based techniques provide a sensitive and robust analytical platform for the analysis of plant-based products.
Digital Object Identifier (DOI)
https://doi.org/10.13023/etd.2022.344
Funding Information
National Science Foundation EPSCor Track 2 (OAI 1632854)
Naprogenix Inc (1R44AA025804 "Mutant transgenic plant cells as a novel source of drugs" from the United States National Institute on Alcohol Abuse and Alcoholism)
Recommended Citation
Dorrani, Masoumeh, "Application Of Mass Spectrometry For Characterization Of Plant-Based Phenolics And Alkaloids" (2022). Theses and Dissertations--Chemistry. 168.
https://uknowledge.uky.edu/chemistry_etds/168
Included in
Agriculture Commons, Analytical Chemistry Commons, Food Chemistry Commons, Organic Chemistry Commons, Wood Science and Pulp, Paper Technology Commons
