离子色谱-质谱联用技术在生命健康领域中的应用进展

doi:10.3724/SP.J.1123.2023.11001

摘要/Abstract

摘要：

离子色谱是一种用于分离强极性和可电离物质的色谱技术,质谱是一种基于离子m/z的分析技术,离子色谱与质谱联用(IC-MS)可用于复杂样品中可电离化合物(包括无机化合物和有机化合物)的分离、鉴定与定量。本文综述了IC-MS技术的发展以及近20年来IC-MS技术在食品分析、药物分析、代谢组学和临床中毒检测等领域的应用进展和未来发展趋势。在食品分析方面,本文主要介绍了IC-MS技术在无机阴离子、有机酸、极性农药、生物胺和糖类等物质检测方面的应用进展;在药物分析方面,本文主要介绍了IC-MS技术在药物杂质分析、药物降解产物鉴定和血药浓度测定领域的研究进展;在代谢组学方面,本文主要介绍了IC-MS技术在生物基质中的有机酸、糖磷酸酯、核苷酸等强极性代谢物分离、分析领域的研究进展;在临床中毒分析方面,本文主要介绍了IC-MS技术在烷基甲基膦酸、甲基膦酸、草甘膦、3-硝基丙酸和茚满二酮类鼠药等强极性或可电离有毒化合物检测方面的应用进展。本文将为IC-MS技术在生命健康领域的进一步拓展和应用提供有益参考。

关键词: 离子色谱-质谱联用, 食品分析, 药物分析, 代谢组学, 临床中毒分析, 综述

Abstract:

Ion chromatography is a technique commonly used to separate strongly polar and ionizable substances; it can be used to separate, identify, and quantify ionizable compounds in complex samples when coupled with mass spectrometry, and is currently being used in the application of food analysis, drug analysis, metabolomics and clinical poisoning analysis. Herein, we review the development of ion chromatography-mass spectrometry (IC-MS), its progress over the past 20 years, and future trends in the abovementioned areas. The IC-MS research progress and applications for the determination of inorganic anions, organic acids, polar pesticides, biogenic amines, and sugars in the food field are discussed. Drug analysis applications are discussed mainly in relation to the analysis of drug impurities, identifying drug degradation products, and determination of plasma concentration, while the separation and analysis of strongly polar metabolites, such as organic acids, sugar phosphates, and nucleotides in biological matrices are discussed in relation to metabolomics. Advances in the analysis of strongly polar or ionizable toxic compounds, such as alkyl methylphosphonic acid, methylphosphonic acid, glyphosate, 3-nitropropionic acid, and indandione rodenticides, are mainly discussed in clinical poisoning analysis field. This paper is expected to become a useful reference for the further expansion and application of IC-MS in the life and health fields.

Key words: ion chromatography-mass spectrometry (IC-MS), food analysis, drug analysis, metabolomics, clinical poisoning analysis, review

中图分类号:

O658

易雨欣, 金米聪. 离子色谱-质谱联用技术在生命健康领域中的应用进展[J]. 色谱, 2024, 42(10): 923-934.

YI Yuxin, JIN Micong. Advances in the application of ion chromatography-mass spectrometry in the fields of life and health[J]. Chinese Journal of Chromatography, 2024, 42(10): 923-934.

图/表 5

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Analytes	Sample types	IC separation column	Elution solvents and elution program	LODs	LOQs	Method
Bromate	bread	IonPac AS10 (250 mm×4 mm)	NaOH solution; gradient elution	6 μg/kg	-	IC-ICP- MS^[10]
Bromate	bread	GL-IC-A15	(NH₄)₂CO₃ solution; isocratic elution	2 μg/kg	5 μg/kg	IC-ICP- MS^[11]
Bromate and bromide	drinking water	IonPac AS19 (250 mm×4 mm)	NH₄NO₃ solution; isocratic elution	bromate: 0.25 μg/L; bromide: 0.20 μg/L	-	IC-ICP- MS^[12]
Bromate	flour products	IonPac AS31 (250 mm×2 mm)	KOH solution; gradient elution	5 μg/kg	17 μg/kg	IC- MS^1[13]
Perchlorate, bromate and iodide	milk	IonPac AS20 (250 mm×2 mm)	KOH solution; isocratic elution	perchlorate: 0.02 μg/L; bromate: 0.1 μg/L; iodide: 0.5 μg/L	-	IC-MS/ MS^[14]
Perchlorate	lettuce and spinach	IonPac AS16 (250 mm×2 mm)	NaOH solution; isocratic elution	0.04 μg/L	-	IC- MS^1[15]
Chlorate and perchlorate	freshly brewed coffee	IonPac AS16 (250 mm×2 mm)	methylamine aqueous solution and acetoni- trile; gradient elution	-	chlorate: 15 μg/L; perchlorate: 1.5 μg/L	IC-MS/ MS^[16]
Perchlorate	foods and beverages	IonPac AS20 (250 mm×2 mm)	KOH solution; gradient elution	0.5 ng/L	-	IC-MS/ MS^[17]
Chlorate and perchlorate	infant formula milk powder	IonPac AS20 (250 mm×2 mm)	KOH solution; gradient elution	chlorate: 1.0 μg/kg; perchlorate: 0.3 μg/kg	chlorate: 3 μg/kg; perchlorate: 1 μg/kg	IC-MS/ MS^[18]
Bromate, chlorate and perchlorate	flour products	IonPac AS16 (250 mm×2 mm)	methylamine aqueous solution and acetoni- trile; gradient elution	bromate: 0.002 mg/kg; chlorate: 0.02 mg/kg; perchlorate: 0.002 mg/kg	bromate: 0.007 mg/kg; chlorate: 0.07 mg/kg; perchlorate: 0.007 mg/kg	IC-MS/ MS^[19]
Perchlorate	tea	IonPac AS20 (250 mm×2 mm)	KOH solution; isocratic elution	1.7 μg/kg	6 μg/kg	IC-MS/ MS^[20]
Perchlorate	tea	IonPac AS19 (250 mm×2 mm)	KOH solution; gradient elution	0.3 μg/kg	1 μg/kg	IC-MS/ MS^[21]

Analytes	Sample types	IC separation column	Elution solvents and elution program	LODs	LOQs	Method
Bromate	bread	IonPac AS10 (250 mm×4 mm)	NaOH solution; gradient elution	6 μg/kg	-	IC-ICP- MS^[10]
Bromate	bread	GL-IC-A15	(NH₄)₂CO₃ solution; isocratic elution	2 μg/kg	5 μg/kg	IC-ICP- MS^[11]
Bromate and bromide	drinking water	IonPac AS19 (250 mm×4 mm)	NH₄NO₃ solution; isocratic elution	bromate: 0.25 μg/L; bromide: 0.20 μg/L	-	IC-ICP- MS^[12]
Bromate	flour products	IonPac AS31 (250 mm×2 mm)	KOH solution; gradient elution	5 μg/kg	17 μg/kg	IC- MS^1[13]
Perchlorate, bromate and iodide	milk	IonPac AS20 (250 mm×2 mm)	KOH solution; isocratic elution	perchlorate: 0.02 μg/L; bromate: 0.1 μg/L; iodide: 0.5 μg/L	-	IC-MS/ MS^[14]
Perchlorate	lettuce and spinach	IonPac AS16 (250 mm×2 mm)	NaOH solution; isocratic elution	0.04 μg/L	-	IC- MS^1[15]
Chlorate and perchlorate	freshly brewed coffee	IonPac AS16 (250 mm×2 mm)	methylamine aqueous solution and acetoni- trile; gradient elution	-	chlorate: 15 μg/L; perchlorate: 1.5 μg/L	IC-MS/ MS^[16]
Perchlorate	foods and beverages	IonPac AS20 (250 mm×2 mm)	KOH solution; gradient elution	0.5 ng/L	-	IC-MS/ MS^[17]
Chlorate and perchlorate	infant formula milk powder	IonPac AS20 (250 mm×2 mm)	KOH solution; gradient elution	chlorate: 1.0 μg/kg; perchlorate: 0.3 μg/kg	chlorate: 3 μg/kg; perchlorate: 1 μg/kg	IC-MS/ MS^[18]
Bromate, chlorate and perchlorate	flour products	IonPac AS16 (250 mm×2 mm)	methylamine aqueous solution and acetoni- trile; gradient elution	bromate: 0.002 mg/kg; chlorate: 0.02 mg/kg; perchlorate: 0.002 mg/kg	bromate: 0.007 mg/kg; chlorate: 0.07 mg/kg; perchlorate: 0.007 mg/kg	IC-MS/ MS^[19]
Perchlorate	tea	IonPac AS20 (250 mm×2 mm)	KOH solution; isocratic elution	1.7 μg/kg	6 μg/kg	IC-MS/ MS^[20]
Perchlorate	tea	IonPac AS19 (250 mm×2 mm)	KOH solution; gradient elution	0.3 μg/kg	1 μg/kg	IC-MS/ MS^[21]

Analytes	Sample types	IC separation column	Elution solvents and elution program	LODs	LOQs	Method
Citric acid	wine	IonPac AS20 (50 mm× 2 mm)	KOH solution; gradient elution	17.6 μg/L	-	IC- M
Quinic acid, lactic acid, acetic acid, formic acid, iso-butyric acid, pyruvic acid, iso-valeric acid, valeric acid, malic acid, succinic acid, malonic acid, tartaric acid, maleic acid, oxalic acid, α-ketoglutaric acid, fumaric acid, citric acid, iso-citric acid, cis-aconitic acid and trans-aconitic acid	juices and beverages	IonPac AS11-HC (250 mm× 2 mm)	KOH solution (containing 10% methanol); gradient elution	0.05-0.5 mg/L	-	IC- MS^1[23]
Malic acid, tartaric acid, citric acid, glycolic acid, lactic acid and mandelic acid	fresh juice	IonPac AS11-HC (250 mm× 2 mm)	KOH solution; gradient elution	malic acid, tartaric acid and citric acid: 0.002 mg/L; glycolic acid: 0.015 mg/L; lactic acid: 0.005 mg/L; mandelic acid: 0.025 mg/L	-	IC- MS^1[24]
D-(-)-Quinic acid, L-pyroglutamate acid, lactic acid, formic acid, pyruvic acid, succinate acid, malic acid, propanedioic acid, D-tartaric acid, maleic acid, α-ketoglutaric acid, oxalic acid, fumaric acid, orthophosphoric acid, citric acid and trans-aconitic acid	fermented yoghurt, cereal beverage, chinkiang vinegar, fruit juice and red wine	Homemade separation column (250 mm× 1.0 mm)	NaOH solution; gradient elution	0.01-0.22 mg/L	0.03- 0.8 mg/L	IC- M
Oxalic acid, fumaric acid, maleic acid, malic acid, tartaric acid, citric acid, quinic acid, aconitic acid, succinic acid and lactic acid	liquor, yellow rice wine and dry red wine	IonPac AS11-HC (250 mm× 4 mm)	KOH solution; gradient elution	1.0-8.0 μg/L	3.5- 26.5 μg/L	IC-MS/ MS^[26]

Analytes	Sample types	IC separation column	Elution solvents and elution program	LODs	LOQs	Method
Citric acid	wine	IonPac AS20 (50 mm× 2 mm)	KOH solution; gradient elution	17.6 μg/L	-	IC- M
Quinic acid, lactic acid, acetic acid, formic acid, iso-butyric acid, pyruvic acid, iso-valeric acid, valeric acid, malic acid, succinic acid, malonic acid, tartaric acid, maleic acid, oxalic acid, α-ketoglutaric acid, fumaric acid, citric acid, iso-citric acid, cis-aconitic acid and trans-aconitic acid	juices and beverages	IonPac AS11-HC (250 mm× 2 mm)	KOH solution (containing 10% methanol); gradient elution	0.05-0.5 mg/L	-	IC- MS^1[23]
Malic acid, tartaric acid, citric acid, glycolic acid, lactic acid and mandelic acid	fresh juice	IonPac AS11-HC (250 mm× 2 mm)	KOH solution; gradient elution	malic acid, tartaric acid and citric acid: 0.002 mg/L; glycolic acid: 0.015 mg/L; lactic acid: 0.005 mg/L; mandelic acid: 0.025 mg/L	-	IC- MS^1[24]
D-(-)-Quinic acid, L-pyroglutamate acid, lactic acid, formic acid, pyruvic acid, succinate acid, malic acid, propanedioic acid, D-tartaric acid, maleic acid, α-ketoglutaric acid, oxalic acid, fumaric acid, orthophosphoric acid, citric acid and trans-aconitic acid	fermented yoghurt, cereal beverage, chinkiang vinegar, fruit juice and red wine	Homemade separation column (250 mm× 1.0 mm)	NaOH solution; gradient elution	0.01-0.22 mg/L	0.03- 0.8 mg/L	IC- M
Oxalic acid, fumaric acid, maleic acid, malic acid, tartaric acid, citric acid, quinic acid, aconitic acid, succinic acid and lactic acid	liquor, yellow rice wine and dry red wine	IonPac AS11-HC (250 mm× 4 mm)	KOH solution; gradient elution	1.0-8.0 μg/L	3.5- 26.5 μg/L	IC-MS/ MS^[26]

Analytes	Sample types	IC separation column	Elution solvents and elution program		LOQs	Method
Chlorate, ethephon, fosetyl-aluminium, glufosinate, glyphosate, N-acetyl aminomethyl phosphonic acid, N-acetyl glyphosate, perchlorate and phosphonic acid	fruit and vegetables	IonPac AS19 (250 mm× 2 mm)	KOH solution; gradient elution	-	-	IC-MS/ MS^[27]
Chlorate, perchlorate, ethephon and 2-hydroxyethylphosphonic acid	plant-derived commodities	Metrosep A Supp 5 (150 mm×2 mm)	NH₄HCO₃ solu- tion and acetoni- trile; gradient elution	-	-	IC-MS/ MS^[28]
Glyphosate, glufosinate and bentazone	tea	IonPac AS20 (250 mm× 4 mm)	NaOH solution; gradient elution	0.11-0.39 μg/L	0.36-1.30 μg/L	IC-MS/ MS^[29]
Fosetyl and phosphonic acid	tomato, apple, lemon, sultana, avocado and wheat	Metrosep A Supp 5 (150 mm×2 mm)	NH₄HCO₃ solu- tion and acetoni- trile; gradient elution	-	10 μg/kg	IC-MS/ MS^[30]
Glyphosate, aminomethyl phosphonic acid, N-acetyl aminomethyl phosphonic acid, glufosinate, 3-methylphosphinicopropionic acid, N-acetyl glufosinate, ethephon, chlorate, perchlorate, fosetyl aluminium and phosphonic acid	cereals, grapes and infant food	IonPac AS19 (250 mm× 2 mm)	KOH solution; gradient elution	-	0.01-100 mg/kg	IC-MS/ MS^[31]
Ethephon and 2,4-dichlorophenoxyacetic acid	eggplant, tomato, corn and chili	IonPac AS19 (250 mm× 4 mm)	KOH solution; isocratic elution	ethephon: 0.2 μg/kg; 2,4- dichloropheno- xyacetic acid: 0.05 μg/kg	ethephon: 0.7 μg/kg; 2,4- dichloropheno- xyacetic acid: 0.17 μg/kg	IC-MS/MS^[32]
Glyphosate, glufosinate and aminomethylphosphonic acid	honey, fish and bovine muscle	IonPac AS19 (250 mm× 2 mm)	KOH solution; gradient elution	-	4.30-9.26 μg/kg	IC-HRMS^[33]
Glyphosate and aminomethylphosphonic acid	honey	IonPac AS19 (250 mm× 2 mm)	KOH solution; gradient elution	-	glyphosate: 0.005 mg/kg; aminom- ethyl phosphonic acid: 0.02 mg/kg	IC-HRMS^[34]
Paraquat, difenzoquat, diquat, mepiquat and chlormequat	mineral water, beef, juice and tea	IonPac CS17 (15 mm× 2 mm)	formic acid, acetonitrile and water; gradient elution	chlormequat, difenzoquat and mepiquat: 1.5 μg/L; diquat and paraquat: 3 μg/L	chlormequat, difenzoquat and mepiquat: 5 μg/L; diquat and paraquat: 10 μg/L	IC-HRMS^[35]
Pentachlorophenol, 2-chlorophenol, 4-chlorophenol, 3-chlorophenol, 2,6-dichlorophenol, 2,3-dichlorophenol, 2,5-dichlorophenol, 2,4-dichlorophenol, 3,4-dichlorophenol, 3,5-dichlorophenol, 2,3,5-trichlorophenol, 2,4,5-trichlorophenol, 2,4,6-trichlorophenol and 3,4,5-trichlorophenol	clam tissues	IonPac AS11 (250 mm× 4 mm)	KOH solution and acetonitrile; gradient elution	-	0.05-0.50 μg/kg	IC-MS^1[36]