Simultaneous analysis of kasugamycin and streptomycin in vegetables by liquid chromatography-tandem mass spectrometry

Abstract

In this work an LC-MS/MS method has been developed for the simultaneous analysis of kasugamycin (KAS) and streptomycin (STR) in vegetable samples. The use of a mixed-mode HPLC column and a ternary mobile phase acetonitrile:water:0.5% aqueous formic acid in gradient elution mode are proposed to provide enough retention and resolution for these highly polar compounds. Heated-electrospray ionization (H-ESI) has been used to ionize KAS and STR when coupling liquid chromatography to mass spectrometry.In contrast to what happens with most aminoglycosides, KAS only showed singly charged ions in the full-scan mass spectrum. The [M + H] + of both KAS and STR are proposed as precursor ions for tandem mass spectrometry since more stable product ions and better ion ratio precisions are obtained.Fragmentation of KAS has been studied, showing that the cleavage of the glycosidic bonds provided the main product ions and the most abundant and selective ones are proposed for quantitation and confirmation purposes in MRM mode. The LC-MS/MS method developed has been applied to the analysis of vegetables. A simple clean-up procedure using hydrophilic-lipophilic-balanced cartridges was applied to several vegetable extracts from tomato, zucchini, chard and lettuce, obtaining recoveries >80% for both compounds. The high matrix suppression observed for KAS in all matrices was reduced by a 1 : 5 sample dilution with acetonitrile, providing a 100-fold improvement in sensitivity for this compound. Method quality parameters have been established for tomato matrices, obtaining method limits of quantitation in the low mg kg À1 level (5-10 mg kg À1 ) for both compounds, precisions expressed in %RSD better than 7% and accuracies expressed as relative error better than 8% at the 100 mg kg À1 level, making this method suitable for routine analysis.

HLB-MCX-Based Solid-Phase Extraction Combined with Liquid Chromatography–Tandem Mass Spectrometry for the Simultaneous Determination of Four Agricultural Antibiotics (Kasugamycin, Validamycin A, Ningnanmycin, and Polyoxin B) Residues in Plant-Origin Foods

“…Hence, it has been a great challenge to establish an analysis method of antibiotics in complex matrices and meet the requirement of low MRLs. In this case, high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC–MS/MS) has become an ideal choice and is intensively employed for the identification and quantification of agricultural antibiotics in foods. ,,,,− However, insufficient retention on reversed-phase LC columns is still a problem due to the strong hydrophilic properties. Generally, strategies like the addition of ion-pairing agents in the mobile phase, hydrophilic interaction liquid chromatography (HILIC), ,,, or their combination were proposed to achieve enough retention for highly polar compounds.…”

Polymer‐spray mass spectrometric detection and quantitation of hydrophilic compounds and some narcotics

“…Figure shows the total‐ion current (TIC) and mass spectra of 1000 μg/mL streptomycin deposited at a volume of 2 μL (2‐μg loading). As seen in Figure , streptomycin peaks are observed when a spray voltage of 5 kV is applied to the OSX polymer wetted with 20 μL of 1:1 (v/v) methanol/water spray solvent: the singly and doubly charged ions, [M + 2H] 2+ ( m/z 291.63) and [M + H] + ( m/z 582.27), arise from protonation and the singly and doubly charged ions are from the hydrated form of the aldehyde group [M + H 2 O + H] + ( m/z 600.28) and [M + H 2 O + 2H] 2+ ( m/z 300.64), respectively . The methanol adduct, [M + MeOH + H] + ( m/z 614.29), is also observed.…”

“…The observed product ions are similar to what has been reported using liquid chromatography/tandem mass spectrometry. 27…”

Development of an Analytical Method for Kasugamycin Residue in Herbal Medicine, <i>Achyranthes japonica</i> Nakai

“…As a result of comparing and analyzing the resolution and sensitivity of kasugamycin through C18, HILIC, and amide columns for HPLC analysis, the C18 column was rapidly eluted without staying in the column due to the amino group of kasugamycin, and it was not easy to separate it from the interfering material, as shown in Fig. 1(a) [11,19]. The HILIC column acts effectively on polar basic compounds and aminoglycosides, but its retention time was short, and peak tailing was confirmed, which required improvement, as seen in Fig.…”

“…A study of simultaneous analysis of agricultural fungicides using an HLB SPE cartridge and MCX SPE cartridge was reported. The simultaneous analysis of kasugamycin and validamycin-A through a consecutive cleanup process combined HLB SPE cartridge and SCX SPE cartridge as described in previous studies [8], and simultaneous analysis of kasugamycin and streptomycin in five vegetables was reported [11].…”