Isohumulones, the main bittering agents in beer, are decomposed by light-induced reactions, thereby leading to radical precursors on the pathway to lightstruck flavour formation. Excited flavins, formed on visible-light irradiation, readily interact with isohumulones, as well as with reduced and oxidized derivatives thereof. From identification of both volatile and non-volatile reaction products thus formed, feasible degradation mechanisms are proposed.
Flavin mononucleotide (FMN, as a B(2) vitamin model) was shown to induce dimerization of flavonoids (flavanone, apigenin, naringenin, eriodictyol, taxifolin, catechin, kaempferol, luteolin, quercetin, rutin, and seven smaller model phenols studied) as the major photoreaction, when aqueous solutions were exposed to visible light using a new, real-time electrospray ionization mass-spectrometric (ESI-MS) technique supported by LC-MS and MS(2) analysis. Electrophilic intermediates such as transient radical cations, o-quinones, and p-quinone methide were proposed to be involved in the coupling process. The C(3)-OH in flavon-3-ols gave rise to atypical compounds such as a depside or a dioxane-linked dimer. Flavonoid dimers, formed in vegetal extracts added to food during storage in light and for which structures are proprosed based on MS and MS(2), may affect colloidal stability, color, astringency, and antioxidative capacity.
A capillary LC-MS/MS system was evaluated for the absolute quantification of enkephalins in cerebrospinal fluid (CSF). On column focusing on a C18 trapping column, in-line with the analytical column, was used for preconcentration. Quantification was performed with a triple quadrupole instrument in the multiple reaction monitoring mode. Weighted linear regression analysis proves to be a good linearity in a dynamic range of two orders of magnitude. The method was validated, yielding calibration curves with correlation coefficients greater than 0.9914. Assay precision and accuracy were evaluated by direct injection of enkephalin fortified artificial CSF (aCSF) samples at three concentration levels. Mean accuracy of analysed concentrations was between 97.63 and 107.6%. LOD and LOQ were assessed at, respectively, 0.5 and 1 pmol/mL. Validation results show that it is feasible, with a capillary LC-MS/MS system, to quantify neuropeptides in the low femtomole range in aCSF. The obtained coefficients of variation, however, indicate that the use of appropriate isotopically labelled internal standards in neuropeptide quantification using narrow bore LC, combined with ESI-MS, may be highly beneficial.
This article describes a simple method to perform lock mass corrected accurate mass measurements in tandem mass spectrometry (MS/MS) with a quadrupole time-of-flight (Q-TOF) mass spectrometer. The experimental approach consists of using the protonated molecule of a known compound, which is measured in a MS/MS function using low collision energy (no fragmentation), as mass calibrator. The unknown compound is acquired in MS/MS mode albeit using high collision energy. After the acquisition, the two MS/MS spectra of unknown and mass calibrator are combined, and the fragments of the unknown are lock mass corrected by using the protonated molecule of the mass calibrator. To prove this concept, 10 compounds were analyzed using this approach, the fragments interpreted and, where possible, related to structural data available in the literature. All the unequivocally assigned fragments were accurately mass measured with mass errors within appropriate limits, i.e. for m/z values <200 with a mass tolerance of 3 mDa while for m/z > 200 the mass tolerance is expressed as 10 ppm.
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