20α- and 20β-dihydrocortisone may interfere in LC-MS/MS determination of cortisol in saliva and urine

2017 ◽  
Vol 55 (3) ◽  
pp. 341-347 ◽  
Author(s):  
Marlen Israelsson ◽  
Ralph Brattsand ◽  
Göran Brattsand
Keyword(s):  
Original Method ◽  
Fragmentation Pattern ◽  
Phase Gradient ◽  
Late Night ◽  
Low Concentrations ◽  
Mass Spectrometric Fragmentation ◽  
Positive Ion ◽  
Chromatography Step ◽  
Endogenous Steroid

Background LC-MS/MS methods offer high selectivity in cortisol determinations. However, endogenous steroid metabolites may still interfere and compromise the results, for example in the diagnosis of Cushing’s syndrome. Erroneously elevated cortisol may, in particular, be misleading at the low concentrations found in salivary samples obtained at late night and after dexamethasone suppression. Methods Interferences in our LC-MS/MS method used for determination of cortisol in saliva and urine were identified by comparing their retention times and mass spectra with those of pure candidate substances. The chromatographic conditions used in our LC-MS/MS method, including column and mobile phase gradient, were varied in order to separate the target compound from the interferences. Results Two interferences, which were co-eluting or eluting close to cortisol in our original method, were successfully separated from cortisol by adjustment of the chromatographic conditions. These interferences were found in both urine and saliva and were identified as the two endogenous cortisol isomers 20α- and 20β-dihydrocortisone. The isomers share molecular mass and mass spectrometric fragmentation pattern with cortisol using electrospray ionization in the positive-ion mode. Both give rise to the transitions m/z 363.1>121.1, 363.1>115.1 and 363.1>97.1. In our original LC-MS/MS setup, the 20β-dihydrocortisone co-eluted with cortisol in the chromatography step resulting in false high determinations. Conclusions Cortisol determination by LC-MS/MS may suffer from erroneously elevated results unless 20α- and 20β-dihydrocortisone are chromatographically separated from cortisol.

scholarly journals Determination of macroline and tetracyclines group in water by liquid chromatography tandem mass spectrometry (LC-MS/MS)

2020 ◽  
Vol 3 (3) ◽  
pp. 173-182
Author(s):  
Trong Le Van ◽  
Thanh Hang Nguyen Thi ◽  
Huy Do Quang ◽  
Khai Nguyen Manh ◽  
◽  
...  
Keyword(s):  
Liquid Chromatography ◽  
High Accuracy ◽  
Method Detection Limit ◽  
Chromatography Tandem Mass Spectrometry ◽  
Low Concentrations ◽  
Liquid Chromatography Tandem Mass ◽  
Trace Concentrations ◽  
Positive Ion ◽  
Tetracycline Group

Antibiotics are contaminants at low concentrations and found in water with the range of ng/L. Determination of antibiotics at trace concentrations requires modern and high accuracy equipment. Liquid chromatography mass tandem spectrometry (LC-MS/MS) able to determine contaminants at ppt and ppb levels, which is suitable for quantification of the macrolide and tetracycline group in water. The Analytical method using Agilent Triple Quard 6460 LC-MS/MS system with positive ion mode. Agilent XDB C18 column (1.8 µm × 2.1 × 100 mm) and Agilent Eclipse SDB C18 pre-column (2.1 × 5 mm × 1.8 µm) were used. Mobile phase was acetonitrile and HCOOH 0.1%. Samples were cleaned with Oasis PRiME HLB 3cc SPE column (150 mg). The method was evaluated based on specificity, recovery, repeatability and estimation of the uncertainty. The method detection limit (MDL) for the analytes is 0.03 µg/L. Recovery ranges from 85.23 -117.70%; repeatability (RSDr) is between 2.20% and 12.45%.

scholarly journals Rapid Preparation of a Large Sulfated Metabolite Library for Structure Validation in Human Samples

Metabolites ◽  
2020 ◽  
Vol 10 (10) ◽  
pp. 415 ◽  
Author(s):  
Mario S. P. Correia ◽  
Weifeng Lin ◽  
Arash J. Aria ◽  
Abhishek Jain ◽  
Daniel Globisch
Keyword(s):  
Chemical Synthesis ◽  
Synthesis Method ◽  
Metabolite Identification ◽  
Research Field ◽  
Fragmentation Pattern ◽  
Rapid Preparation ◽  
Human Sample ◽  
Mass Spectrometric Fragmentation ◽  
Time Information

Metabolomics analysis of biological samples is widely applied in medical and natural sciences. Assigning the correct chemical structure in the metabolite identification process is required to draw the correct biological conclusions and still remains a major challenge in this research field. Several metabolite tandem mass spectrometry (MS/MS) fragmentation spectra libraries have been developed that are either based on computational methods or authentic libraries. These libraries are limited due to the high number of structurally diverse metabolites, low commercial availability of these compounds, and the increasing number of newly discovered metabolites. Phase II modification of xenobiotics is a compound class that is underrepresented in these databases despite their importance in diet, drug, or microbiome metabolism. The O-sulfated metabolites have been described as a signature for the co-metabolism of bacteria and their human host. Herein, we have developed a straightforward chemical synthesis method for rapid preparation of sulfated metabolite standards to obtain mass spectrometric fragmentation pattern and retention time information. We report the preparation of 38 O-sulfated alcohols and phenols for the determination of their MS/MS fragmentation pattern and chromatographic properties. Many of these metabolites are regioisomers that cannot be distinguished solely by their fragmentation pattern. We demonstrate that the versatility of this method is comparable to standard chemical synthesis. This comprehensive metabolite library can be applied for co-injection experiments to validate metabolites in different human sample types to explore microbiota-host co-metabolism, xenobiotic, and diet metabolism.

Simultaneous Determination of Alogliptin, Linagliptin, Saxagliptin, and Sitagliptin in Bulk Drug and Formulation by UPLC Q-TOF-MS

2020 ◽  
Vol 17 (1) ◽  
pp. 95-105
Author(s):  
Ramji Rathod ◽  
Faraat Ali ◽  
Amrish Chandra ◽  
Robin Kumar ◽  
Meenakshi Dahiya ◽  
...  
Keyword(s):  
Internal Standard ◽  
Gradient Elution ◽  
Ultra Performance Liquid Chromatography ◽  
Pharmaceutical Dosage Forms ◽  
Sensitivity And Selectivity ◽  
The Mean ◽  
Bulk Drug ◽  
Positive Ion ◽  
Higher Sensitivity

Background: A simple and sensitive Ultra Performance Liquid Chromatography-Mass Spectrometry method was developed and validated to measure the concentrations of Alogliptin (ALO), Linagliptin (LIN), Saxagliptin (SAX), and Sitagliptin (SIT) using Pioglitazone (PIO) as an internal standard. Methods: Chromatographic separation of six gliptins was achieved on a C-18 column (100×2.1 mm, 2.7 μm) using a mobile phase consisting of formic acid in water, 0.1%v/v: acetonitrile in gradient elution. Electrospray ionization (ESI) source was operated in the positive ion mode. Targeted MS/MS mode on a QTOF MS was used to quantify the drug utilizing the transitions of 340.1(m/z), 473.2 (m/z), 316.2 (m/z), 408.1 (m/z), and 357.1 (m/z) for ALO, LIN, SAX, SIT and PIO respectively. Results: As per ICH Q2R1 guidelines, a detailed validation of the method was carried out and the standard curves were found to be linear over the concentration ranges of 1516.0-4548.1 ng mL-1, 519.8- 1559.4 ng mL-1, 1531.4-4594.3 ng mL-1and 1519.6-4558.8 ng mL-1 for ALO, LIN, SAX and SIT respectively. Precision and accuracy results were within the acceptable limits. The mean recovery was found to be 98.8 _ 0.76 % (GEM), 102.2 _ 1.59 % (LIN), 95.3 _ 2.74 % (SAX) and 99.2 _ 1.75 % (SIT) respectively. Conclusions: The optimized validated UPLC QTOF-MS/MS method offered the advantage of shorter analytical times and higher sensitivity and selectivity. The optimized method is suitable for application in quantitative analysis of pharmaceutical dosage forms for QC laboratory.

scholarly journals The Double Face of Ketamine—The Possibility of Its Identification in Blood and Beverages

Molecules ◽  
2021 ◽  
Vol 26 (4) ◽  
pp. 813
Author(s):  
Magdalena Świądro ◽  
Paweł Stelmaszczyk ◽  
Irena Lenart ◽  
Renata Wietecha-Posłuszny
Keyword(s):  
Date Rape ◽  
Signal To Noise Ratio ◽  
High Sensitivity ◽  
Heroin Addiction ◽  
Assisted Extraction ◽  
Low Concentrations ◽  
High Concentrations ◽  
Rosé Wine ◽  
Tof Ms

The purpose of this study was to develop and validate a high-sensitivity methodology for identifying one of the most used drugs—ketamine. Ketamine is used medicinally to treat depression, alcoholism, and heroin addiction. Moreover, ketamine is the main ingredient used in so-called “date-rape” pills (DRP). This study presents a novel methodology for the simultaneous determination of ketamine based on the Dried Blood Spot (DBS) method, in combination with capillary electrophoresis coupled with a mass spectrometer (CE-TOF-MS). Then, 6-mm circles were punched out from DBS collected on Whatman DMPK-C paper and extracted using microwave-assisted extraction (MAE). The assay was linear in the range of 25–300 ng/mL. Values of limits of detection (LOD = 6.0 ng/mL) and quantification (LOQ = 19.8 ng/mL) were determined based on the signal to noise ratio. Intra-day precision at each determined concentration level was in the range of 6.1–11.1%, and inter-day between 7.9–13.1%. The obtained precision was under 15.0% (for medium and high concentrations) and lower than 20.0% (for low concentrations), which are in accordance with acceptance criteria. Therefore, the DBS/MAE/CE-TOF-MS method was successfully checked for analysis of ketamine in matrices other than blood, i.e., rose wine and orange juice. Moreover, it is possible to identify ketamine in the presence of flunitrazepam, which is the other most popular ingredient used in DRP. Based on this information, the selectivity of the proposed methodology for identifying ketamine in the presence of other components of rape pills was checked.

scholarly journals Wine origin authentication linked to terroir – wine fingerprint

2019 ◽  
Vol 15 ◽  
pp. 02033
Author(s):  
B. Gabel
Keyword(s):  
Pore Water ◽  
Isotope Composition ◽  
Food Product ◽  
Isotopic Signature ◽  
Original Method ◽  
Economic Problem ◽  
Red Wines ◽  
Table Grapes ◽  
Mineral Phases

Global wine and alcohol trade faces a serious economic problem linked to counterfeiting of these commodities. Recently applied authentication methods and techniques pose more difficulties for counterfeiters but they are apparently not effective once we consider economical losses identified by EU legal authorities. The presented solution links isotopic characteristics of the soil, plant, technological intermediate product and the final food product (wine, grapes) on the basis of 87Sr/86Sr isotopes ratios. For the isotopic signature of wines, the average isotope composition of the substrate cannot be a reliable indicator. Only the isotopic composition of pore water can, as it leaches various mineral phases at different stages and passes into vine root system. Instead of complicated sampling of pore water, an original method of preparing and processing soil samples and consequently must & wine samples was developed. Based on both, soil and biological material analysis, we can unquestionably determine not only geographical but also regional and local authenticity of the wine. Determination of red wines isotopic signature is more straightforward process in comparison to white wines, because of technologically different processing of grapes. That is the reason why, in case of white vines, the 87Sr/86Sr ratio of bentonites (natural purifier and absorbent useful in the process of winemaking) must also be taken into consideration. Results of analyses of Slovak wines from geographically diverse regions as well as from sites in close-by distances have clearly established reliability of presented concept, in which the soil is linked to the plant and to the final food product (wine or table grapes).

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