Display omitted
•Two tandem MS techniques were applied to structural speciation of CGAs in Ferrovia Italian sweet cherry.•Some methylcoumaroyl and caffeoylquinates were found in cherries for the ...first time.•trans-3-O-Coumaroylquinic and chlorogenic acids were the main CGAs quantified.
This paper deals with an extensive analytical approach, which uses two complementary tandem mass spectrometry techniques, to characterize the chlorogenic acids (CGAs) present in a typical Italian sweet cherry variety (cv Ferrovia). Sixteen monoacyl-quinic acids and esters, five diacyl-quinic acids, three caffeoyl-quinic acids glycosides, and two caffeic acid hexoses were detected by HPLC-MSn analyses (MSn up to MS4), among which four methyl coumaroyl quinate and three methyl caffeoyl quinate isomers were tentatively identified in sweet cherries for the first time. HPLC-MS/MS analyses through multiple reaction monitoring (MRM) experiments showed that trans-3-O-caffeoylquinic acid, cis-3-O-coumaroylquinic acid, trans-3-O-coumaroylquinic acid, trans-5-O-caffeoylquinic acid, and methyl-3-O-caffeoyl quinate were the main CGAs in the mature berries of cv Ferrovia. Considering that CGAs can have several health benefits depending on their amount but also on their structural features, the results of this study provide new insight into the knowledge of the quali-quantitative profile of these phytochemicals in a widespread fruit such as sweet cherry.
Objective
Polycystic ovary syndrome (PCOS) is a pathophysiological disease affecting reproductive and metabolic indicators. Research has shown that kisspeptin might be involved in the regulation of ...pituitary hormone secretion and energy metabolism. The aim of this study was to investigate the relationship between serum kisspeptin levels and abnormal metabolism in PCOS.
Methods
Fifty patients with PCOS and 50 control patients were recruited for this study. Serum kisspeptin levels were measured via ELISA. High‐performance liquid chromatography‐tandem mass spectrometry metabolomics was used to study the changes in serum metabolism between the PCOS and control groups.
Results
Serum kisspeptin levels were significantly elevated in individuals with PCOS compared with those in healthy controls (p = 0.011) and positively correlated with LH, T, FFA, BA, and LEP levels (p < 0.05). Significantly dysregulated expression of several metabolites was observed in the intergroup comparisons of the high‐kisspeptin PCOS, low‐kisspeptin PCOS, and healthy control groups. These primarily consisted of lipid, amino acid, and carbohydrate metabolites, among which palmitic acid and N‐formylkynurenine levels were lower in the high‐kisspeptin group than in controls. Metabolite set enrichment analysis was also performed based on metabolites in the KEGG database. The results showed that owing to the differences in kisspeptin concentrations in individuals with PCOS, there was a significant difference in amino acid and pyruvate metabolism.
Conclusions
Kisspeptin could be a potential biomarker for the diagnosis of PCOS and plays an important role in metabolic regulation in individuals with PCOS. In addition, metabolomics provides a promising method for the study of metabolic abnormalities in individuals with PCOS, which might contribute to our understanding of its mechanisms.
A multiresidue method for the quantification of 13 sulfonamides in animal feed is described. It involves the application of a modified QuEChERS procedure followed by HPLC–MS/MS (high performance ...liquid chromatography coupled to tandem mass spectrometry) analysis. The best conditions for the extraction solution and PSA (primary secondary amine) mass were determined. After optimization, the method was validated according to the European Commission Decision 2002/657/EC. The validation levels employed were 25, 50 and 75 μg kg−1. Acceptable values were obtained for the following parameters: linearity (0.9864 < r2 < 0.9993), decision limit (50.4 μg kg−1 < CCα < 55.8 μg kg−1), detection capability (50.7 μg kg−1<CCβ < 55.8 μg kg−1), limit of quantification (0.9 μg kg−1 < LOQ < 7.1 μg kg−1), accuracy (86.0 < recovery rates < 106.8), precision (3.6 < repeatability < 19.5), (5.5 < intermediate precision < 21.6), measurement uncertainty (MU) (4.1 < MU < 32.6) and selectivity. These findings met the Codex requirements, which allow for the routine use of the method by the laboratories linked to the Ministry of Agriculture, Livestock and Food Supply of Brazil. Finally, the method was applied to real samples and only one of them showed positive for sulfamethazine, however, with a concentration below the LOQ of the method.
► Food analysis using HPLC–MS. ► Analytical methodology of (tandem) mass spectrometry. ► LC–MS analysis of flavonoids, mycotoxins, pesticides and other components in food. ► LC–MS analysis of ham, ...cheese, milk, cereals, olive oil and wine.
HPLC–MS applications in the agrifood sector are among the fastest developing fields in science and industry. The present tutorial mini-review briefly describes this analytical methodology: HPLC, UHPLC, nano-HPLC on one hand, mass spectrometry (MS) and tandem mass spectrometry (MS/MS) on the other hand. Analytical results are grouped together based on the type of chemicals analyzed (lipids, carbohydrates, glycoproteins, vitamins, flavonoids, mycotoxins, pesticides, allergens and food additives). Results are also shown for various types of food (ham, cheese, milk, cereals, olive oil and wines). Although it is not an exhaustive list, it illustrates the main current directions of applications. Finally, one of the most important features, the characterization of food quality (including problems of authentication and adulteration) is discussed, together with a future outlook on future directions.
Brazil nuts were shelled and separated as kernel and brown skin; whole nuts were also used. Soluble phenolics from each portion as well as the whole nut were extracted using 70% acetone under reflux ...conditions. Insoluble-bound phenolics were subsequently extracted into diethyl ether–ethyl acetate mixture (1:1, v/v) after alkaline hydrolysis. Both soluble and insoluble-bound phenolic extracts were separately examined for their total phenolics content; antioxidant activities were evaluated by trolox equivalent antioxidant capacity (TEAC), 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical and hydroxyl radical scavenging activities using electron paramagnetic resonance (EPR), reducing power, and oxygen radical scavenging capacity (ORAC). Soluble phenolics in brown skin was 1236.07 as compared to 406.83 in kernel and 519.11 mg/100 g in whole nut. Bound phenolics content of brown skin was also 86- and 19-folds higher than kernel and whole nut, respectively. Similarly extracts from the brown skin exhibited the highest antioxidant activity. Free- and bound phenolics were identified and quantified; these included nine phenolic acids and flavonoids and their derivatives (gallic acid, gallocatechin. protocatechuic acid, catechin, vanillic acid, taxifolin, myricetin, ellagic acid, and quercetin). However, some phenolics were present only in the bound form. Furthermore, the phenolics were dominant in the brown skin.
Clinical pharmacokinetic studies of antiretrovirals require accurate and precise measurement of plasma drug concentrations. Here we describe a simple, fast and sensitive HPLC–MS/MS method for ...determination of the commonly used protease inhibitors (PI) amprenavir, atazanavir, darunavir, lopinavir, ritonavir, saquinavir and the non-nucleoside reverse transcriptase inhibitor (NNRTI) nevirapine, as well as the more recent antiretrovirals, the CCR5 antagonist maraviroc and the “second generation” NNRTI etravirine and rilpivirine. An internal standard (quinoxalone; QX) was added to plasma aliquots (100
μl) prior to protein precipitation with acetonitrile (500
μl) followed by centrifugation and addition of 0.05% formic acid (200
μl) to the supernatant. Chromatographic separation was achieved using a gradient (acetonitrile and 0.05% formic acid) mobile phase on a reverse-phase C
18 column. Detection was via selective reaction monitoring (SRM) operating in positive ionization mode on a triple-quadrupole mass spectrometer. All compounds eluted within a 5
min run time. Calibration curves were validated over concentration ranges reflecting therapeutic concentrations observed in HIV-infected patients from pharmacokinetic data reported in the literature. Correlation coefficients (
r
2) exceeded 0.998. Inter- and intra-assay variation ranged between 1% and 10% and % recovery exceeded 90% for all analytes. The method described is being successfully applied to measure plasma antiretroviral concentrations from samples obtained from clinical pharmacokinetic studies.
A new pair of derivatization reagents, d0-4-(1-methyl-1H-phenanthro9,10-dimidazol-2-yl)phenlamine (d0-MPIA) and d3-4-(1-methyl-1H-phenanthro9,10-dimidazol-2-yl)phenlamine (d3-MPIA) have been designed ...and synthesized. It was successfully used to label aliphatic aldehydes and the aldehyde derivatives were analyzed by high-performance liquid chromatography–tandem mass spectrometry (HPLC–MS/MS). The new isotope-coded reagents could easily label aldehydes under acidic conditions in the presence of NaCNBH3. The target derivatives exhibited intense M+H+ and regular product ions with electrospray ionization source in positive mode. The d0/d3-MPIA-aldehydes were monitored by the transitions of M+H+→m/z 322 and M+H+→m/z 165, and the obtained detection limits were in the range of 0.18–15.9pg/mL at signal to noise ratio of 3. The global isotope internal standard technology was employed for quantification analysis with d3-MPIA-aldehyde as internal standard for corresponding d0-MPIA-aldehyde. Excellent linear responses for relative quantification were observed in the range of 1/10–10/1 with coefficients >0.998. The developed method has been applied to the quantification of aliphatic aldehydes in selected aquatic products with RSD<3.6% and recoveries >85.2%.
Display omitted
•A pair of novel isotope-coded derivatization reagent for aliphatic aldehydes was developed.•Aliphatic aldehydes composition in aquatic product was quantified on the basis of isotope-coded strategy by HPLC–MS/MS.•Sensitivity was much enhanced comparing with the reported isotope-coded methods.
Medically important (MI) antibiotics are defined by the United States Food and Drug Administration as drugs containing certain active antimicrobial ingredients that are used for the treatment of ...human diseases or enteric pathogens causing food-borne diseases. The presence of MI antibiotic residues in environmental water is a major concern for both aquatic ecosystems and public health, particularly because of their potential to contribute to the development of antimicrobial-resistant microorganisms. In this article, we present a review of global trends in the sales of veterinary MI antibiotics and the analytical methodologies used for the simultaneous determination of antibiotic residues in environmental water. According to recently published government reports, sales volumes have increased steadily, despite many countries having adopted strategies for reducing the consumption of antibiotics. Global attention needs to be directed urgently at establishing new management strategies for reducing the use of MI antimicrobial products in the livestock industry. The development of standardized analytical methods for the detection of multiple residues is required to monitor and understand the fate of antibiotics in the environment. Simultaneous analyses of antibiotics have mostly been conducted using high-performance liquid chromatography–tandem mass spectrometry with a solid-phase extraction (SPE) pretreatment step. Currently, on-line SPE protocols are used for the rapid and sensitive detection of antibiotics in water samples. On-line detection protocols must be established for the monitoring and screening of unknown metabolites and transformation products of antibiotics in environmental water.
Display omitted
•Trends in global sales of medically important veterinary antibiotics are surveyed.•Analytical methods for detection of veterinary antibiotics in water are reviewed.•Sample pretreatment methods and analytical conditions are reviewed.•HPLC-MS/MS is one of the most powerful and frequently used analytical methods.•Solid-phase extraction pretreatment can increase selectivity and reproducibility.
The recycling and revalorization of wastes from the agri-food industry (AFI) have emerged in the scientific scenario as a multidisciplinary working field in the framework of the circular bioeconomy. ...Residues and side materials from AFI result in a great source of raw products with increasing social and economic impact. In this regard, phenolic compounds are possibly the most relevant group of phytochemicals from AFI wastes because of their multiple healthy properties, including antioxidant, anti-inflammatory, hypolipidemic, and antibacterial activities. Among other sources, olive oil, winemaking, and fruit and vegetable juice wastes have been considered to assess their revalorization. The paper reviews the recovery and characterization of AFI waste extracts to generate by-products rich in polyphenols for chemical, nutraceutical, and food science applications. Polyphenols are recovered from AFI waste by solvent extraction with conventional and advanced techniques. The resulting extracts are complex, and the major phenolic compounds should be identified and quantified. The profiling of analytes such as proanthocyanins, curcuminoids, resveratrol derivatives, caffeic acids, and oleuropein is often performed by liquid chromatography with UV/Vis or fluorescence detection. Additionally, liquid chromatography coupled to mass spectrometry is the technique of choice for the unambiguous identification of target compounds and structural elucidation of new and unknown molecules. Complementarily, the antioxidant activity of the extracts can be determined using spectrophotometric assays.
PDF
