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ARS Home » Midwest Area » Peoria, Illinois » National Center for Agricultural Utilization Research » Functional Foods Research » Research » Publications at this Location » Publication #325834

Research Project: Evaluation of the Chemical and Physical Properties of Low-Value Agricultural Crops and Products to Enhance Their Use and Value

Location: Functional Foods Research

Title: The ETD-like fragmentation for small molecules

item HUGUET, ROMAIN - Thermo Fisher Scientific
item WEISBROD, CHAD - Thermo Fisher Scientific
item Berhow, Mark
item ZABROUSKOV, VLAD - Thermo Fisher Scientific
item SCHWARTZ, JAE - Thermo Fisher Scientific
item STRATTON, TIM - Thermo Fisher Scientific

Submitted to: Meeting Abstract
Publication Type: Abstract Only
Publication Acceptance Date: 6/5/2016
Publication Date: 5/9/2016
Citation: Huguet, R., Weisbrod, C., Berhow, M.A., Zabrouskov, V., Schwartz, J., Stratton, T. 2016. The ETD-like fragmentation for small molecules [abstract]. American Society for Mass Spectrometry.

Interpretive Summary:

Technical Abstract: Introduction (137) Flavonoids are a class of plant and fungus secondary metabolites (three-ring structure C6-C3-C6 with various substitutions) involved in many functions such as pigmentation, UV filtration, symbiotic nitrogen fixation, cell cycle inhibitors, and defense mechanisms. These polyphenolic antioxidants have been incorporated for thousands of years in Eastern medicine but have yet to be utilized in Western therapeutics despite their phenomenal record in providing health benefits. For example, regular consumption of flavonoids may reduce the risk of death from coronary heart disease for elderly people. An increasing number of studies today are investigating their biological properties, many with a focus on the connection between their antioxidant activity and their chemical structures. Here we investigate the molecular structures of several flavonoids using a set of various fragmentation techniques (CID, HCD, and UVPD) available on a modified Orbitrap Fusion Lumos Tribrid. Method (60) In this study, we performed direct infusion experiments of various flavones and conjugated flavonoids with a modified Orbitrap Fusion Lumos Tribrid MS. We performed CID, HCD, and UVPD fragmentation experiments on these molecules for structural investigation. The data acquired from the different fragmentation techniques were used to reveal the molecular structures of each flavonoid using mzCloud and Xcalibur Qual Browser. Preliminary Data (160) The preliminary tests performed with the flavone Robinin showed that UVPD experiments provided much more informative MS/MS spectral information than the other dissociation techniques. Common fragment ions using all three techniques were observed (331.1000, 617.1477, 471.0903, 308.0291, and 185.0420) but the UVPD option also provided unique fragmentation channels in both low (no limitation with low mass cut-off as observed with CID) and high mass range: 121.0283, 149.0231, and 763.204. These preliminary results present UVPD technique as a potential tool in the structural elucidation of conjugated flavonoid structures especially as CID and HCD fragmentation techniques are severely limited for flavonoid aglycones, O-glycosides, C-glycosides, and acylated glycosides characterization. The diversity of chemical space in conjugated flavanoids is extremely large with the total number of combinations of conjugate sugars on different cores and their linking positions being unknown. UVPD definitely offers the ability to gain unique fragmentation information which could lead to the position of conjugation that could be the key for identification. Novel Aspect (23) The new UVPD is a unique and unmatched fragmentation process required for complete and accurate molecular structural elucidation of flavonoids and conjugated flavonoids.