Rapid screening of sulfonamides in dietary supplements based on extracted common ion chromatogram and neutral loss scan by LC-Q/TOF-mass spectrometry

Nam-Yong Ki; Jisu Hur; Beom Hee Kim; Kyung Ho Kim; Bong Jin Moon; Han Bin Oh; Jongki Hong

doi:10.1016/j.jfda.2018.08.006

Rapid screening of sulfonamides in dietary supplements based on extracted common ion chromatogram and neutral loss scan by LC-Q/TOF-mass spectrometry

J Food Drug Anal. 2019 Jan;27(1):164-174. doi: 10.1016/j.jfda.2018.08.006. Epub 2018 Sep 28.

Authors

Nam-Yong Ki¹, Jisu Hur¹, Beom Hee Kim¹, Kyung Ho Kim², Bong Jin Moon³, Han Bin Oh³, Jongki Hong¹

Affiliations

¹ College of Pharmacy, Kyung Hee University, Seoul 02447, South Korea.
² College of Pharmacy, Kangwon National University, Chunchun 24341, South Korea.
³ Department of Chemistry, Sogang University, Seoul 04107, South Korea.

Abstract

There is an increasing amount of dietary supplements that are adulterated with diuretics and anti-diabetic drugs; this has become a global problem due to the wide distribution of dietary supplements and the serious negative health effects of the adulterants. In this study, a rapid screening method was developed for detection and confirmation of 35 sulfonamides in supplements by ultra-high performance liquid chromatography quadrupole/time of flight mass spectrometry. For effective extraction of sulfonamides from dietary supplements, four extraction protocols including HLB and WAX solid-phase extraction, Quick Easy Cheap Effective Rugged and Safe method, and pH-controlled liquid-liquid extraction were evaluated, and pH-controlled liquid-liquid extraction method was shown to be the most effective with high recovery efficiency and low matrix effect. Rapid separation of 35 sulfonamides was achieved with the UHPLC C18 column (150 × 2.1 mm, 1.7 um) within 7 min using ammonium acetate aqueous solution (pH 8) and acetonitrile as the mobile phase. From the MS/MS spectra of sulfonamides, common ions (m/z 77.9650 [SO₂N]^- and m/z 79.9812 [SO₂NH₂]^-) and neutral molecule loss fragments (HCl and SO₂) were observed according to their structural characteristics. Extracted common ion chromatograms and neutral loss scan of these characteristic fragments could effectively apply for rapid screening of sulfonamides in various types of supplements. A reduced mass tolerance window of ±5 ppm was useful for detecting targeted and untargeted sulfonamides and could avoid false positive and false negative results. Overall calibration curves within dynamic range for all targets were shown to be linear with a correlation coefficient R² > 0.995 and limits of detection ranged from 0.04 to 11.18 ng/g for all sulfonamides. The established method was successfully applied for screening and confirmation of sulfonamides in various supplements. The developed method will be helpful for the identification of sulfonamide diuretics and anti-diabetics in dietary supplements, promoting public health and consumer safety.

Keywords: Dietary supplements; Extracted common ion chromatogram; Neutral loss scan; Sulfonamides; UHPLC-Q/TOF-MS.

Publication types

Evaluation Study
Research Support, Non-U.S. Gov't

MeSH terms

Chromatography, High Pressure Liquid / methods*
Dietary Supplements / analysis*
Diuretics / analysis
Drug Contamination
Hypoglycemic Agents / analysis
Mass Spectrometry / methods*
Solid Phase Extraction
Sulfonamides / analysis*
Sulfonamides / isolation & purification

Substances

Diuretics
Hypoglycemic Agents
Sulfonamides

Grants and funding

This study was financially supported by the Ministry of Food and Drug Safety of Korea (2018, 18182MFDS425) and the National Research Foundation of Korea (NRF-2017R1A2B4005616).