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The relationship between the electrospray ionization (ESI)-mass spectrometric (MS) response of an analyte and its concentration has been well studied for permanently charged and basic analytes in the positive ionization mode, but there has been a lack of research effort for other analytes, and for the negative ionization mode, in general. In this study, this relationship was investigated for various adducts and deprotonated species of glucose, sucrose, and raffinose using a continuous stirred tank reactor (CSTR) coupled with ESI-tandem MS to obtain a continuum of response factors across a wide concentration range in both the positive and negative ionization modes with a single injection under 18 different combinations of solvents and additives. Profiles of response factors vs. concentrations varied widely and were dependent upon the analyte and solvent parameters. The use of ammonium trifluoroacetate resulted in the highest response factors for methanol-based and acetonitrile-based solvents in the positive and negative ionization modes, respectively. Ammonium acetate, ammonium formate, and sodium chloride in 80:20 acetonitrile:water in the negative ionization mode resulted in good linearities, useful for quantitative analysis. In the positive ionization mode, response factors tended to increase with an increase in the molecular weight of the analyte, and acetonitrile was generally found to decrease response factors. We have also demonstrated the ability of CSTR-ESI-MS to visualize ionization suppression in the presence of co-analytes. These data should be useful for liquid chromatography-ESI-MS method development for sugar analysis, to help guide the choice of mobile phase that will result in high sensitivity and linearity.Graphical Abstract [ABSTRACT FROM AUTHOR]

Thermally accelerated oxidative degradation of aqueous quercetin at pH 5.9 and 7.4 was kinetically measured using an in-house built online continuous flow device made of concentric capillary tubes, modified to fit to the inlet of an electrospray ionization-ion trap-time-of-flight-mass spectrometer (ESI-IT-TOF-MS). Time-resolved mass spectral measurements ranging from 2 to 21 min were performed in the negative mode to track intermediate degradation products and to evaluate the degradation rate of the deprotonated quercetin ion, [Q-H]. Upon heating solutions in the presence of dissolved oxygen, degradation of [Q-H] was observed and was accelerated by an increase in pH and temperature. Regardless of the condition, the same degradation pathways were observed. Degradation mechanisms and structures were determined using higher order tandem mass spectrometry (up to MS) and high mass accuracy. The observed degradation mechanisms included oxidation, hydroxylation, and ring-cleavage by nucleophilic attack. A chalcan-trione structure formed by C-ring opening after hydroxylation at C2 was believed to be a precursor for other degradation products, formed by hydroxylation at the C2, C3, and C4 carbons from attack by nucleophilic species. This resulted in A-type and B-type ions after cross-ring cleavage of the C-ring. Based on time of appearance and signal intensity, nucleophilic attack at C3 was the preferred degradation pathway, which generated 2,4,6-trihydroxymandelate and 2,4,6-trihydroxyphenylglyoxylate ions. Overall, 23 quercetin-related ions were observed. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]