离子色谱在中草药成分分析中的应用

doi:10.3724/SP.J.1123.2023.10009

摘要/Abstract

摘要：

离子色谱是用于分离分析不同基质样品中离子性物质的一种新型高效液相色谱技术。自1975年发展至今,已被广泛应用于环境、能源、食品、医药等多个领域,具有操作简单、分析快速、灵敏度和选择性高,且能同时分离测定多种组分等优点。近年来,随着离子色谱技术自身迭代发展,可测定分析的样品种类已包括离子、糖类、氨基酸、有机酸(碱)等,同时离子色谱法也越来越成为针对中草药复杂组分中单个有效成分分析与鉴定的重要手段。本文介绍了离子色谱技术的不同类型、原理及研究进展,整理了近几十年离子色谱在中草药糖苷类、氨基酸、蛋白质、无机盐以及有机酸、生物碱类和黄酮类等复杂成分中的应用情况;检索文献发现,离子交换色谱、电导检测法为离子色谱中最常用的技术类型和检测方式,且目前离子色谱在生物碱类成分分析中的应用展现出较传统分析方法更好的优势,但在无机阴离子的形态分析和黄酮类、苯丙素类、甾体类等主要活性物质中的直接应用研究报道较少。最后,综述了离子色谱(联用)新技术及其在中草药中的最新进展,并对该色谱方法未来在复杂组分分离分析方面的应用进行了探讨和展望,为离子色谱技术分析中草药复杂化学成分的进一步发展提供理论参考。

关键词: 离子色谱, 中草药, 复杂组分, 成分分析

Abstract:

Ion chromatography (IC) is a novel high performance liquid chromatographic technique that is suitable for the separation and analysis of ionic substances in different matrix samples. Since 1975, it has been widely used in many fields, such as the environment, energy, food, and medicine. IC compensates for the separation limitations of traditional gas chromatography and high performance liquid chromatography and can realize the qualitative analysis and quantitative detection of strongly polar components. This chromatographic technique features not only simple operations but also rapid analysis. The sensors used in IC are characterized by high sensitivity and selectivity, and the technique can simultaneously separate and determine multiple components. Several advances in IC instrumentation and chromatographic theories have been developed in recent years. IC can analyze various types of samples, including ions, sugars, amino acids, and organic acids (bases). Chinese herbal medicines are typically characterized by highly complex chemical compositions and may contain carbohydrates, proteins, alkaloids, and other active components. They also contain toxic residues such as sulfur dioxide, which may be produced during the processing of medicinal materials. Therefore, the analysis and elucidation of the precise chemical constituents of Chinese herbal medicines present key problems that must be resolved in modern Chinese herbal medicine research. In this context, IC has become an important method for analyzing and identifying the complex components of Chinese herbal medicines because this method is suitable for detecting a single active ingredients among complex components.

This paper introduces the different types and principles of IC as well as research progress in this technique. As the applications of IC-based methods in pharmaceutical science, cell biology, and microbiology increase, further development is necessary to expand the applications of this technique. The development of innovative techniques has enabled IC technologies to achieve higher analytical sensitivity, better selectivity, and wider application. The components of Chinese herbal medicines can be divided into endogenous and exogenous components according to their source: endogenous components include glycosides, amino acids, and organic acids, while exogenous components include toxic residues such as sulfur dioxide. Next, the applications of IC to the complex components of Chinese herbal medicines in recent decades are summarized. The most commonly used IC technologies and methods include ion exchange chromatography and conductivity detection. The advantages of IC for the analysis of alkaloids have been demonstrated. This method exhibits better characteristics than traditional analytical methods. However, the applications of IC for the speciation analysis of inorganic anions are limited. Moreover, few reports on the direct application of the technique for the determination of the main active substances in Chinese herbal medicines, including flavonoids, phenylpropanoids, and steroids, have been reported.

Finally, this paper reviews new IC technologies and their application progress in Chinese herbal medicine, focusing on their prospects for the effective separation and analysis of complex components. In particular, we discuss the available sample (on-line) pretreatment technologies and explore possible technologies for the selective and efficient enrichment and separation of different components. Next, we assess innovative research on solid-phase materials that can improve the separation effect and analytical sensitivity of IC. We also describe the features of multidimensional chromatography, which combines the advantages of various chromatographic techniques. This review provides a theoretical reference for the further development of IC technology for the analysis of the complex chemical components of Chinese herbal medicines.

Key words: ion chromatography (IC), Chinese herbal medicine, complex components, component analysis

中图分类号:

O658

张保鑫, 田景琴, 柴国柱, 贺文琪, 兰小中, 韩兴昊. 离子色谱在中草药成分分析中的应用[J]. 色谱, 2024, 42(4): 311-326.

ZHANG Baoxin, TIAN Jingqin, CHAI Guozhu, HE Wenqi, LAN Xiaozhong, HAN Xinghao. Applications of ion chromatography for the analysis of Chinese herbal medicine components[J]. Chinese Journal of Chromatography, 2024, 42(4): 311-326.

图/表 4

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No.	Sources	Analytes				Columns			Eluents^*			Detection			IC type			Ref.
1	Arabidopsis thaliana	glucosides (sugar phosphates)				Dionex CarboPac PA1, CarboPac PA1 guard			E1: 75 mmol/L NaOH, E2: 75 mmol/L NaOH, 500 mmol/L NaAc			ECAM (PAD)			IEC			[37]
2	aloes	glucosides (fucose, rhamnose, arabinose, galactose, glucose, mannose, xylose)				Dionex CarboPac PA10			14-20 mmol/L NaOH			ECAM (integrated PAD)			IEC			[38]
3	Cistanches herba	glucosides (fucose, rhamnose, arabinose, galactose, glucose, mannose, xylose, fructose, ribose)				Dionex Carbopac PA210-Fast-4μm			20, 200 mmol/L NaOH			ECAM (integrated PAD)			IEC			[39]
4	Xanthii Fructus	glucosides (carboxyatractyloside, atractylodis)				Agilent Eclipse XDB-C18			ACN-0.15% NaH₂PO₄ (containing 0.12% TBAH, adjusted to pH 3.5 with H₃PO₄)			UV-Vis (203 nm)			IPC			[41]
5	Lonicerae Japonicae flos, Forsythiae fructus, Sectellarlae radix	amino acids				Hitachi 2622 SC			5 buffer solutions			UV-Vis (570, 440 nm)			IEC			[46]
6	Hedysari Radix	amino acids (aspartic acid, serine, histidine, etc.)				LCA K 06/Na			A: pH 3.45 CPBS, B: pH 10.85 CP-BBS, C: 0.02% EDTA alkaline solution			UV-Vis (570, 440 nm)			IEC			[47]
7	mixed standard solution	amino acids (leucine, taurine, phenylalanine)				AG4A-SC(DX-100T IC)			0.75 mmol/L KCl+ NaOH (pH 11.5)			suppressor CD			IEC			[48]
8	mixed standard solution	amino acid (threonine)				Metrosep C2-150			4 mmol/L tartaric acid, 1 mmol/L DPA			direct CD			IEC			[49]
9	mixed standard solution	amino acids				AminoPac PA10			60-200 mmol/L NaOH, 400 mmol/L NaAc			ECAM (PAD)			IEC			[50]
10	Anoectochilus roxburghii	amino acids (arginine, alanine, glycine, valine etc.)				Dionex AminoPac PA10			A: water, B: 250 mmol/L NaOH, C: 1 mol/L NaAc			ECAM (PAD)			IEC			[52]
11	18 medicinal plant samples	amino acids (19 species)				Dionex Acclaim^TM RSLC Polar Advantage Ⅱ			A: water containing 1% ACN-0.5% HFBA- 0.02% TFA, B: ACN containing 0.1% TFA			IC-MS			IPC			[54]
12	Nigella sativa	proteins				DEAE-Sephadex A50			50 mmol/L PBS (pH 6.4), 0.01-2 mol/L NaCl			UV-Vis (280 nm)			IEC			[57]
13	Liparis nervosa	protein (mannose-binding lectin)				DEAE-Sepharose			50 mmol/L PBS (pH 8.5), 0-1 mol/L NaCl			UV-Vis (280 nm)			IEC			[58]
14	Amorphophallus paeoniifolius	protein (tyrosinase)				DEAE-cellulose			50 mmol/L PBS (pH 6.0), 0-300 mmol/L NaCl			UV-Vis (280 nm)			IEC			[59]
15	Gypsum- Anemarrhenae composite	metal cations (Na⁺, K⁺, Mg²⁺, Ca²⁺)				IonPac CS12A			20 mmol/L MSA			suppressor CD			IEC			[65]
16	Rhizoma chuanxiong, Semen zizyphi spinosae	metal cations (Na⁺, N, K⁺, Mg²⁺, Ca²⁺)				ICS-C25			2.5 mmol/L pyromellitic acid			suppressor CD			IEC			[66]
17	oral preparations		metal cations (Na⁺, K⁺, Mg²⁺)				Dionex^® IonPac^® CS16			A: 6.7% MSA aqueous solution, B: water			suppressor CD			IEC			[67]
18	Jinyinhua		metal cations (K⁺, Na⁺, Mg²⁺, Ca²⁺)				IonPac CS12A			20 mmol/L MSA			suppressor CD			IEC			[68]
19	Melilotus officinalis		inorganic anions (Cl^-, N, S)				Dionex IonPac AS22			ultrapure water- NaHCO₃ (1.5 mmol/L)- Na₂CO₃ (4.5 mmol/L)			suppressor CD			IEC			[69]
20	Danshen injection		inorganic anions (F^-, HCOO^-, Cl^-, Br^-, N, N)				IonPac AS11-HC			12-20 mmol/L KOH solution			suppressor CD			IEC			[70]
21	Panax notoginseng		inorganic anion (Cl^-)				IonPac AS15			30 mmol/L KOH solution			suppressor CD			IEC			[71]
22	Ligusticum chuanxiong		inorganic anions (H₂P, Cl^-, N)				Shim-pack IC-A1			potassium hydrogen phthalate solution			direct CD			IEC			[72]
23	Angelicae sinensis radix		microelements (Sb(V, Ⅲ))				IonPac AS14			50 mmol/L DAP- 50 mmol/L tartaric acid (pH 6.5)			IC-BEcHG-AFS			IEC			[74]
24	Asini corii colla		microelement (Cr(Ⅵ))				IonPac AS19			30 mmol/L KOH solution			UV (545 nm)			IEC			[75]
25	Tricholomamatsutake		microelement (As)				Dionex IonPac AS7			A: 2.5 mmol/L (NH₄)₂CO₃, B: 100 mmol/L (NH₄)₂CO₃			IC-ICP-MS			IEC			[76]
26	Chenxiang Huaqi pill		microelements (As(Ⅲ, V), Cr(Ⅵ))				IonPac AS7, IonPac AG7			5-100 mmol/L (NH₄)₂- CO₃, 0.76 mmol/L NH₄NO₃(pH 9.3)			IC-ICP-MS			IEC			[77]
27	Jasminum sambac, Glycyrrhizae radix et rhizoma, Citri reticulatae pericarpium, etc.		inorganic anions (F^-, Cl^-, N, S, P)				self-assembly (YSA-4A model)			water, 4 mmol/L NaHCO₃-2 mmol/L Na₂CO₃ solution			direct CD			IEC			[78]
28	Coptis herbs		organic acids (quinic acid, acetic acid, formic acid, tartaric acid, malic acid, succinic acid, oxalic acid)				IonPac AS11-HC			1-60 mmol/L KOH solution			suppressor CD			IEC			[83]
29	Fructus mume herbs		organic acids (lmalic acid, oxalic acid, fumaric acid, citric acid)				Dionex IonPac AS19			4-54 mmol/L KOH solution			suppressor CD			IEC			[84]
30	Ganoderma lucidum		organic acids (oxalic acid, tartaric acid, malic acid, glycolic acid)				Transgenomic ICSep Ion 300			8 mmol/L H₂SO₄ solution			suppressor CD			IEC			[85]
31	Shengmai injection		organic acids (citric acid, malic acid, succinic acid)				Transgenomic Sep- ION-300			5 mmol/L H₂SO₄- acetone (95∶5, v/v)			suppressor CD			ICE			[86]
32	rice wine		organic acids (13 kinds of oxalic acid, tartaric acid, ascorbic acid, etc.)				IC-Pak Ion Exclusion			H₂SO₄-ACN (98∶2, v/v)			UV (210 nm)			ICE			[87]
33	Ephedrae herba		alkaloid (ephedrine hydrochloride)				Dionex AG9-HC			8 mmol/L Na₂CO₃- MeOH (9∶1, v/v)			ECAM (DC amperometric detection)			IEC			[94]
34	molasses		alkaloid (betaine)				WY-Cation-1			2 mmol/L MSA			direct CD			IEC			[95]
35	Zuojin pill		alkaloids (13 kinds of berberine hydrochloride, palmatine hydrochloride, evodiamine, rutaecarpine, etc.)				Diamonsil C18			A: 1.5 mmol/L SDS (adjust pH 5.0 with H₃PO₄), B: ACN			UV (265 nm)			IPC			[96]
36	compound Kushen injection			alkaloids (matrine, oxymatrine, sophocarpine, oxysophocarpine)	Diamonsil C18			A: 0.04% H₃PO₄- 10 mmol/L sodium pentanesulfonate aqueous solution, B: ACN			UV (210 nm)			IPC			[97]
37	Uncaria sessilifructus			alkaloid (total alkaloids)	PhenoSphere SCX			A: 20 mmol/L NH₄OAc- 0.05% formic acid aqueous solution, B: MeOH			UV (254, 203 nm)			IEC			[98]
38	Atractylodis macrocephalae rhizoma, Dioscoreae rhizoma, Armeniacae semen amarum, Lonicerae flos, etc.			sulfur dioxide residue	IonPac@AS11-HC			20 mmol/L KOH solution			suppressor CD			IEC			[110]
39	Rhei radix et rhizoma			sulfur dioxide residue	IonPac AS18			NaOH solution			suppressor CD			IEC			[111]
40	bitter almond, Persicae semen			sulfur dioxide residue	Dionex Ionpac AS11A			12 mmol/L KOH solution			suppressor CD			IEC			[112]
41	Gastrodiae rhizoma			sulfur dioxide residue	A-SUPP5-150			3.2 mmol/L Na₂CO₃ solution, 1 mmol/L NaHCO₃ solution			suppressor CD			IEC			[113]
42	chicory roots			sulfur dioxide residue	IonPac AS-11-HC			20 mmol/L KOH solution			suppressor CD			IEC			[114]

No.	Sources	Analytes				Columns			Eluents^*			Detection			IC type			Ref.
1	Arabidopsis thaliana	glucosides (sugar phosphates)				Dionex CarboPac PA1, CarboPac PA1 guard			E1: 75 mmol/L NaOH, E2: 75 mmol/L NaOH, 500 mmol/L NaAc			ECAM (PAD)			IEC			[37]
2	aloes	glucosides (fucose, rhamnose, arabinose, galactose, glucose, mannose, xylose)				Dionex CarboPac PA10			14-20 mmol/L NaOH			ECAM (integrated PAD)			IEC			[38]
3	Cistanches herba	glucosides (fucose, rhamnose, arabinose, galactose, glucose, mannose, xylose, fructose, ribose)				Dionex Carbopac PA210-Fast-4μm			20, 200 mmol/L NaOH			ECAM (integrated PAD)			IEC			[39]
4	Xanthii Fructus	glucosides (carboxyatractyloside, atractylodis)				Agilent Eclipse XDB-C18			ACN-0.15% NaH₂PO₄ (containing 0.12% TBAH, adjusted to pH 3.5 with H₃PO₄)			UV-Vis (203 nm)			IPC			[41]
5	Lonicerae Japonicae flos, Forsythiae fructus, Sectellarlae radix	amino acids				Hitachi 2622 SC			5 buffer solutions			UV-Vis (570, 440 nm)			IEC			[46]
6	Hedysari Radix	amino acids (aspartic acid, serine, histidine, etc.)				LCA K 06/Na			A: pH 3.45 CPBS, B: pH 10.85 CP-BBS, C: 0.02% EDTA alkaline solution			UV-Vis (570, 440 nm)			IEC			[47]
7	mixed standard solution	amino acids (leucine, taurine, phenylalanine)				AG4A-SC(DX-100T IC)			0.75 mmol/L KCl+ NaOH (pH 11.5)			suppressor CD			IEC			[48]
8	mixed standard solution	amino acid (threonine)				Metrosep C2-150			4 mmol/L tartaric acid, 1 mmol/L DPA			direct CD			IEC			[49]
9	mixed standard solution	amino acids				AminoPac PA10			60-200 mmol/L NaOH, 400 mmol/L NaAc			ECAM (PAD)			IEC			[50]
10	Anoectochilus roxburghii	amino acids (arginine, alanine, glycine, valine etc.)				Dionex AminoPac PA10			A: water, B: 250 mmol/L NaOH, C: 1 mol/L NaAc			ECAM (PAD)			IEC			[52]
11	18 medicinal plant samples	amino acids (19 species)				Dionex Acclaim^TM RSLC Polar Advantage Ⅱ			A: water containing 1% ACN-0.5% HFBA- 0.02% TFA, B: ACN containing 0.1% TFA			IC-MS			IPC			[54]
12	Nigella sativa	proteins				DEAE-Sephadex A50			50 mmol/L PBS (pH 6.4), 0.01-2 mol/L NaCl			UV-Vis (280 nm)			IEC			[57]
13	Liparis nervosa	protein (mannose-binding lectin)				DEAE-Sepharose			50 mmol/L PBS (pH 8.5), 0-1 mol/L NaCl			UV-Vis (280 nm)			IEC			[58]
14	Amorphophallus paeoniifolius	protein (tyrosinase)				DEAE-cellulose			50 mmol/L PBS (pH 6.0), 0-300 mmol/L NaCl			UV-Vis (280 nm)			IEC			[59]
15	Gypsum- Anemarrhenae composite	metal cations (Na⁺, K⁺, Mg²⁺, Ca²⁺)				IonPac CS12A			20 mmol/L MSA			suppressor CD			IEC			[65]
16	Rhizoma chuanxiong, Semen zizyphi spinosae	metal cations (Na⁺, N, K⁺, Mg²⁺, Ca²⁺)				ICS-C25			2.5 mmol/L pyromellitic acid			suppressor CD			IEC			[66]
17	oral preparations		metal cations (Na⁺, K⁺, Mg²⁺)				Dionex^® IonPac^® CS16			A: 6.7% MSA aqueous solution, B: water			suppressor CD			IEC			[67]
18	Jinyinhua		metal cations (K⁺, Na⁺, Mg²⁺, Ca²⁺)				IonPac CS12A			20 mmol/L MSA			suppressor CD			IEC			[68]
19	Melilotus officinalis		inorganic anions (Cl^-, N, S)				Dionex IonPac AS22			ultrapure water- NaHCO₃ (1.5 mmol/L)- Na₂CO₃ (4.5 mmol/L)			suppressor CD			IEC			[69]
20	Danshen injection		inorganic anions (F^-, HCOO^-, Cl^-, Br^-, N, N)				IonPac AS11-HC			12-20 mmol/L KOH solution			suppressor CD			IEC			[70]
21	Panax notoginseng		inorganic anion (Cl^-)				IonPac AS15			30 mmol/L KOH solution			suppressor CD			IEC			[71]
22	Ligusticum chuanxiong		inorganic anions (H₂P, Cl^-, N)				Shim-pack IC-A1			potassium hydrogen phthalate solution			direct CD			IEC			[72]
23	Angelicae sinensis radix		microelements (Sb(V, Ⅲ))				IonPac AS14			50 mmol/L DAP- 50 mmol/L tartaric acid (pH 6.5)			IC-BEcHG-AFS			IEC			[74]
24	Asini corii colla		microelement (Cr(Ⅵ))				IonPac AS19			30 mmol/L KOH solution			UV (545 nm)			IEC			[75]
25	Tricholomamatsutake		microelement (As)				Dionex IonPac AS7			A: 2.5 mmol/L (NH₄)₂CO₃, B: 100 mmol/L (NH₄)₂CO₃			IC-ICP-MS			IEC			[76]
26	Chenxiang Huaqi pill		microelements (As(Ⅲ, V), Cr(Ⅵ))				IonPac AS7, IonPac AG7			5-100 mmol/L (NH₄)₂- CO₃, 0.76 mmol/L NH₄NO₃(pH 9.3)			IC-ICP-MS			IEC			[77]
27	Jasminum sambac, Glycyrrhizae radix et rhizoma, Citri reticulatae pericarpium, etc.		inorganic anions (F^-, Cl^-, N, S, P)				self-assembly (YSA-4A model)			water, 4 mmol/L NaHCO₃-2 mmol/L Na₂CO₃ solution			direct CD			IEC			[78]
28	Coptis herbs		organic acids (quinic acid, acetic acid, formic acid, tartaric acid, malic acid, succinic acid, oxalic acid)				IonPac AS11-HC			1-60 mmol/L KOH solution			suppressor CD			IEC			[83]
29	Fructus mume herbs		organic acids (lmalic acid, oxalic acid, fumaric acid, citric acid)				Dionex IonPac AS19			4-54 mmol/L KOH solution			suppressor CD			IEC			[84]
30	Ganoderma lucidum		organic acids (oxalic acid, tartaric acid, malic acid, glycolic acid)				Transgenomic ICSep Ion 300			8 mmol/L H₂SO₄ solution			suppressor CD			IEC			[85]
31	Shengmai injection		organic acids (citric acid, malic acid, succinic acid)				Transgenomic Sep- ION-300			5 mmol/L H₂SO₄- acetone (95∶5, v/v)			suppressor CD			ICE			[86]
32	rice wine		organic acids (13 kinds of oxalic acid, tartaric acid, ascorbic acid, etc.)				IC-Pak Ion Exclusion			H₂SO₄-ACN (98∶2, v/v)			UV (210 nm)			ICE			[87]
33	Ephedrae herba		alkaloid (ephedrine hydrochloride)				Dionex AG9-HC			8 mmol/L Na₂CO₃- MeOH (9∶1, v/v)			ECAM (DC amperometric detection)			IEC			[94]
34	molasses		alkaloid (betaine)				WY-Cation-1			2 mmol/L MSA			direct CD			IEC			[95]
35	Zuojin pill		alkaloids (13 kinds of berberine hydrochloride, palmatine hydrochloride, evodiamine, rutaecarpine, etc.)				Diamonsil C18			A: 1.5 mmol/L SDS (adjust pH 5.0 with H₃PO₄), B: ACN			UV (265 nm)			IPC			[96]
36	compound Kushen injection			alkaloids (matrine, oxymatrine, sophocarpine, oxysophocarpine)	Diamonsil C18			A: 0.04% H₃PO₄- 10 mmol/L sodium pentanesulfonate aqueous solution, B: ACN			UV (210 nm)			IPC			[97]
37	Uncaria sessilifructus			alkaloid (total alkaloids)	PhenoSphere SCX			A: 20 mmol/L NH₄OAc- 0.05% formic acid aqueous solution, B: MeOH			UV (254, 203 nm)			IEC			[98]
38	Atractylodis macrocephalae rhizoma, Dioscoreae rhizoma, Armeniacae semen amarum, Lonicerae flos, etc.			sulfur dioxide residue	IonPac@AS11-HC			20 mmol/L KOH solution			suppressor CD			IEC			[110]
39	Rhei radix et rhizoma			sulfur dioxide residue	IonPac AS18			NaOH solution			suppressor CD			IEC			[111]
40	bitter almond, Persicae semen			sulfur dioxide residue	Dionex Ionpac AS11A			12 mmol/L KOH solution			suppressor CD			IEC			[112]
41	Gastrodiae rhizoma			sulfur dioxide residue	A-SUPP5-150			3.2 mmol/L Na₂CO₃ solution, 1 mmol/L NaHCO₃ solution			suppressor CD			IEC			[113]
42	chicory roots			sulfur dioxide residue	IonPac AS-11-HC			20 mmol/L KOH solution			suppressor CD			IEC			[114]