Qualitative and Quantitative Screening of 114 Illegally Added Adulterants in Health Products by High Resolution Four-Stage Electrostatic Field Orbital Trap Mass Spectrometry
LI Yue, LI Min, JI Hong, ZHANG Xian*
Analysis of Chinese Medicines and Biological Evaluation of Beijing Municipal Key Laboratory, Beijing Institute for Drug Control, Beijing 102206, China
Abstract：OBJECTIVE To establish a new qualitative and quantitative screening method for 114 illegal adulterants in traditional Chinese medicine for health care based on high performance liquid chromatography (HPLC) coupled with high four-stage electrostatic field orbital well tandem mass spectrometry. METHODS Using 0.1% formic acid aqueous solution-acetonitrile as mobile phase, gradient elution was performed on SHISEIDO CAPCELL PAK C18 column(3.0 mm×100 mm,3 μm)with column temperature of 40 ℃ and flow rate of 0.3 mL·min-1. The gradient elution program was as follows: 0-18 min, acetonitrile was from 2% to 100%; 18-23 min, acetonitrile was 100%; 23.1-25 min, acetonitrile was 2%. The mass spectrometry was carried out with electrospray ionization source, four stage electrostatic field track mass spectrometry as mass analyzer, and scanning range m/z 120-750, spray voltage 3.5 kV, sheath pressure (N2) 275.8 kPa, auxiliary air pressure (N2) 68.95 kPa. High resolution and high quality mass spectrometry data of parent ions and fragment ions were obtained simultaneously by one injection. The structures of illegal additions were further confirmed by the accurate mass of secondary mass spectrometry. RESULTS This method could simultaneously detect 114 kinds of illegally added chemical drugs of 11 categories including tranquilizers, hormones, slimming, hypoglycemic, hypotensive, lipid-lowering, psychotropic, antiviral, antitussive, analgesic and aphrodisiac drugs within 25 min. The linear range, sensitivity, repeatability and recovery rate all met the requirements of analysis. CONCLUSION The screening method established by four-stage electrostatic field orbital trap mass spectrometry coupled with HPLC is fast, convenient, accurate and retrospective, and can meet the needs of screening confirmation for target and non-target illegal additions.
李岳, 李珉, 纪宏, 张宪. 利用高分辨四级杆静电场轨道阱质谱快速定性和定量筛查确证中药保健品中的114种非法添加药物[J]. 中国药学杂志, 2019, 54(21): 1804-1816.
LI Yue, LI Min, JI Hong, ZHANG Xian. Qualitative and Quantitative Screening of 114 Illegally Added Adulterants in Health Products by High Resolution Four-Stage Electrostatic Field Orbital Trap Mass Spectrometry. Chinese Pharmaceutical Journal, 2019, 54(21): 1804-1816.
GONG L P, TIAN Z Y, GUO C C, et al. Rapid screening and quantitative detection of 24 illegally added anti-inflammatory painkillers in traditiongal Chinese mediciones and health foods by ultra performance liquid chromatography-quadrupole/electrostaticfield orbitrap high resolution mass spectrometry[J]. Chin Pharm J(中国药学杂志), 2015, 50(24):2154-2159.
[2]
ZHANG Y, YANG Z, ZHU R J, et al. Determination of thirty antihypertensive chemical medicines adulterateds in traditional Chinese patent medicines and health foods by UPLC-MS /MS[J]. Chin Pharm J(中国药学杂志), 2012, 47(2):141-145.
[3]
LIU Y W, ZOU Y H, YIN H M, et al. Identification of a tadalafil analogue based on Q-TOF-MS[J]. Chin Pharm J(中国药学杂志), 2016, 51(23):2059-2062.
[4]
WANG Q, SU J, TAN H, et al. Determination of eleven antidiabetics illegally adulterated into Chinese patent drugs and health foods by TLC[J]. Chin Pharm Aff(中国药事), 2010, 24(7):647.
[5]
XU J H, ZHANG R L, SONG X Y, et al. The determination of 11 chemical antidiabetic material in antidiabetics of Chinese traditional medicine by HPLC[J]. Drug Stand China(中国药品标准), 2010, 11(5):335.
[6]
YU H, HU Q, SUN J, et al. Qualitative analysis of illegally adulterated sidenafil and related compounds in dietary supplements by ultra-high performance liquid chromatography-quadrupole-time-of-flight mass spectrometry[J]. Chin J Chromatogr(色谱), 2018, 36(10):1005-1017.
[7]
SUN J, HU Q, FENG R, et al. Determination of 30 antiimpotence compounds illegally adulterated in health products by ultrahigh performance liquid chromatography-triple quadrupole mass spectrometry[J]. J Instrum Anal(分析测试学报), 2018, 37(4):419-426.
[8]
GONG X, LU L, FENG Y L, et al. Fast screening of 25 illegally added chemical drugs in weight-reducing,lipid-lowering and hypoglycemic health foods by HPLC-IT-TOF-MS[J]. China Pharm(中国药师), 2018, 21(8):1463-1468.
[9]
ZHAO J L, OU B L, ZHOU Y. Simultaneous determination of 11 chemicals added in itching agents traditional Chinese edicines by UPLC-MS/MS[J]. Chin J Mod Appl Pharm(中国现代应用药学), 2016, 33(12):1558-1562.
[10]
ZHENG W Y, LI Z, CHEN M, et al. LC-MS/MS Detection of illegally added drugs for weight loss and glucose reduction in Chinese patent medicine and health products[J]. J Shenyang Pharm Univ(沈阳药科大学学报), 2018, 35(1):58-66.
[11]
LI X L, CHEN J, YANG C F, et al. Determination of six antilipemic chemicals illegally added in antilipemic functional foods by UPLC-MS/MS[J]. Food Sci(食品科学), 2018, 39(18):320-324.
[12]
LIU Y, DING T, LIAO X Q, et al. Direct determination of 42 chemical drugs illegally added in herbal medicines and dietary supplement by high performance liquid chromatography-quadrurpole/electrostatic field orbitrap high resolution mass spectrometry[J]. Chin J Anal Chem(分析化学), 2016, 44(3):423-429.
[13]
GUO C C, SUN H, SHI F, et al. Highthroughput screening of 13 digestive drugs adulterated illegally in biochemical drugs, chinese patent medicines and dietary supplements by orbitrap high-resolution mass spectrometry[J]. J Instrum Anal(分析测试学报), 2018, 37(3):300-306.
[14]
JIANG S G, GUO C C, SHI F, et al. Application of Q-orbitrap high resolution mass spectrometry to the detection of illegal adulterated antihyperlipidemics in herbal medicines and dietary supplements[J]. Chin J Pharm Anal(药物分析杂志), 2015, 35(8):1447-1452.
2019, Vol. 54 
