College of Pharmacy, Kyung Hee University, Seoul 02447, South Korea.
College of Pharmacy, Kangwon National University, Chunchun 24341, South Korea.
J Food Drug Anal. 2019 Jan;27(1):164-174. doi: 10.1016/j.jfda.2018.08.006. Epub 2018 Sep 28.
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 [SON] and m/z 79.9812 [SONH]) and neutral molecule loss fragments (HCl and SO) 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 R > 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.
有越来越多的膳食补充剂被掺假利尿剂和抗糖尿病药物；由于膳食补充剂的广泛分布以及掺杂物对健康的严重负面影响，这已成为一个全球性问题。在这项研究中，建立了一种超高效液相色谱四极杆/飞行时间质谱法快速筛查膳食补充剂中 35 种磺胺类药物的方法。为了有效地从膳食补充剂中提取磺胺类药物，评估了包括 HLB 和 WAX 固相萃取、简便快速廉价有效稳定坚固环保方法以及 pH 控制液-液萃取在内的四种提取方案，结果表明 pH 控制液-液萃取方法效果最佳，具有高回收率和低基质效应。使用 UHPLC C18 柱（150×2.1mm，1.7μm），在 7min 内，以乙酸铵水溶液（pH 8）和乙腈作为流动相，可实现 35 种磺胺类药物的快速分离。根据磺胺类药物的 MS/MS 谱，观察到常见离子（m/z 77.9650 [SON] 和 m/z 79.9812 [SONH]）和中性分子丢失碎片（HCl 和 SO），根据其结构特征。提取这些特征碎片的常见离子色谱图和中性丢失扫描可有效用于快速筛选各种类型的补充剂中的磺胺类药物。质量亏损窗口的减小±5ppm 对检测目标和非目标磺胺类药物很有用，可以避免假阳性和假阴性结果。对于所有目标，整个动态范围内的校准曲线均呈线性，相关系数 R＞0.995，所有磺胺类药物的检测限范围为 0.04-11.18ng/g。所建立的方法成功地应用于各种补充剂中磺胺类药物的筛选和确证。所开发的方法将有助于识别膳食补充剂中的磺胺类利尿剂和抗糖尿病药物，促进公众健康和消费者安全。
