Investigation of isomeric transformations of chlorogenic acid in buffers and biological matrixes by ultraperformance liquid chromatography coupled with hybrid quadrupole/ion mobility/orthogonal acceleration time-of-flight mass spectrometry.
ABSTRACT Ultraperformance liquid chromatography coupled with hybrid quadrupole/ion mobility/orthogonal acceleration time-of-flight (oa-TOF) mass spectrometry (UPLC-IM-MS) was used to study the isomeric transformations of trans-5-caffeoylquinic acid, an extremely active compound present in multiple vegetables, fruits, and beverages. The UPLC/oa-TOF MS results proved that in phosphate buffer (pH 7.4), plasma, or urine sample, trans-5-caffeoylquinic acid first isomerizes to trans-4-caffeoylquinic acid and then to trans-3-caffeoylquinic acid by intramolecular acyl migration. When exposed to UV light, trans-3-, -4-, and -5-caffeoylquinic acids undergo cis/trans isomerization to form cis isomers. The isomerization was solely dependent on the pH of the matrix, as well as the incubation temperature, and was independent of metabolic enzymes. UPLC-IM-MS results revealed that a reversible cis/trans isomerization of caffeoylquinic acids could also be induced by the electric field in an electrospray source. Thus, understanding the possible role of electric field-induced isomerization of caffeoylquinic acids may help lessen the confusion between gas phase phenomena and liquid state chemistry when applying IM-MS analysis. The comprehensive understanding of caffeoylquinic acid isomerization transformations is crucial for the appropriate handling of samples and interpretation of experimental data.
- SourceAvailable from: Serban MoldoveanuBeitrage zur Tabakforschung International/ Contributions to Tobacco Research 12/2012; 25(4):498-506.
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ABSTRACT: Calafate (Berberis microphylla G. Forst) is a Patagonian barberry very rich in anthocyanins and one of the fruits with the highest levels of these polyphenols. Other phenolic compounds have also been described in calafate berries. However, to the best of our knowledge there is no available information on hydroxycinnamic acid derivatives. The complexity of hydroxycinnamic acids determination in calafate berries, due to their structure similarities and the interference of high anthocyanin concentration is addressed by means of solid liquid extraction, followed by solid phase extraction clean-up on MCX columns and HPLC-DAD-ESI-MS/MS. The optimized extraction, clean-up and HPLC separation method allowed the assignation of identity and quantification of 20 hydroxycinnamic acids from calafate fruits. 5-Caffeoylquinic acid was the main compound found in all the studied samples. Other 13 hydroxycinnamoyl quinic acids and 6 caffeic acid esters with aldaric acid derivatives assigned as glucaric acid were also identified. Moreover, the glucaric-based hydroxycinnamic acid derivatives accounted for almost the half of total content of this kind of phenolic compounds. The total concentration of hydroxycinnamic acids derivatives ranged between 0.32±0.00μmol/g and 8.28±0.01μmol/g. Effect of ripening and geographical location on hydroxycinnamic acid profiles and concentrations are also evaluated. The methodology allows the determination of hydroxycinnamic acids from calafate despite of the high anthocyanin concentrations, showing a much higher concentration of these acids than other widely consumed berries. Thus suggesting that calafate could be considered a very interesting fruit from the point of view of their nutraceutical composition. However, geographical location and ripening have incidence in levels of studied compounds.Journal of Chromatography A 01/2013; · 4.61 Impact Factor
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ABSTRACT: In this paper, a strategy for the detection and structural elucidation of flavonoid glycosides from a complex matrix in a single chromatographic run using U(H)PLC-ESI-IMS-HDMS/MS(E) is presented. This system operates using alternative low and high energy voltages that is able to perform the task of conventional MS/MS in a data-independent way without re-injection of the sample, which saves analytical time. Also, ion mobility separation (IMS) was employed as an additional separation technique for compounds that are co-eluting after U(H)PLC separation. First, the fragmentation of flavonoid standards were analyzed and criteria was set for structural elucidation of flavonoids in a plant extract. Based on retention times, UV spectra, exact mass, and MS fragment characteristics, such as abundances of daughter ions and the presence of radical ions ([Y0-H](-)), a total 19 flavonoid glycosides, of which 8 non-acylated and 11 acylated, were detected and structurally characterized in a cauliflower waste extract. Kaempferol and quercetin were the main aglycones detected while sinapic and ferulic acid were the main phenolic acids. C-glycosides were also found although their structure could not be elucidated. The proposed method can be used as a rapid screening test for flavonoid identification and for routine analysis of plant extracts, such as these derived from cauliflower waste. The study also confirms that agroindustrial wastes, such as cauliflower leaves, could be seen as a valuable source of different bioactive phenolic compounds.Journal of Chromatography A 11/2013; · 4.61 Impact Factor