固相萃取吸附材料在植物激素样品前处理中的应用新进展

doi:10.3724/SP.J.1123.2021.03045

色谱 ›› 2021, Vol. 39 ›› Issue (12): 1281-1290.DOI: 10.3724/SP.J.1123.2021.03045

固相萃取吸附材料在植物激素样品前处理中的应用新进展

林舒婷¹^,², 丁青青³, 张文敏³^,⁴, 张兰³, 卢巧梅¹^,²^,^*()

1.福州大学福建省高校测试中心, 福建福州 350116
2.福州大学环境与资源学院, 福建福州 350116
3.食品安全与生物分析教育部重点实验室, 福州大学化学学院, 福建福州 350116
4.闽江师范高等专科学校化学与生物工程系, 福建福州 350108

收稿日期:2021-04-05 出版日期:2021-12-08 发布日期:2021-11-23
通讯作者: 卢巧梅
作者简介:*Tel:(0591) 22867790,E-mail: luqm@fzu.edu.cn.
基金资助:
国家自然科学基金(21705026);福建省自然科学基金(2021J01632)

Novel adsorption material for solid phase extraction in sample pretreatment of plant hormones

LIN Shuting¹^,², DING Qingqing³, ZHANG Wenmin³^,⁴, ZHANG Lan³, LU Qiaomei¹^,²^,^*()

1. Fujian College Association Instrumental Analysis Center of Fuzhou University, Fuzhou 350116, China
2. College of Environment and Resources, Fuzhou University, Fuzhou 350116, China
3. Key Laboratory for Analytical Science of Food Safety and Biology (Ministry of Education), College of Chemistry, Fuzhou University, Fuzhou 350116, China
4. Division of Chemical and Biological Engineering, Minjiang Teachers College, Fuzhou 350108, China

Received:2021-04-05 Online:2021-12-08 Published:2021-11-23
Contact: LU Qiaomei
Supported by:
National Natural Sciences Foundation of China(21705026);Natural Science Foundation of Fujian Province(2021J01632)

摘要/Abstract

摘要：

植物激素在植物生长过程中具有重要作用,调节植物生长、发育及抗逆的各个过程。植物激素超微精准定量分析一直是植物生理学研究的瓶颈问题。植物激素的准确、高效检测目前大多是基于液相色谱-串联质谱联用技术。样品前处理是植物激素色谱-质谱分析中必不可少的一个步骤,直接影响后续检测方法的灵敏度和准确性。在植物激素各种前处理方法中,固相萃取(SPE)技术应用非常广泛。在萃取小柱基础上发展了多种新形式(分散固相萃取、磁性固相萃取、固相微萃取等,称之为SPE相关方法)。在上述SPE相关方法中,吸附材料的选择均是关键因素,决定了样品前处理过程的目标物提取、净化和富集效果。碳基材料(包括碳纳米管、石墨烯、碳氮化合物等)和有机骨架材料(包括金属有机骨架、共价有机材料)拥有结构可设计、比表面积大、稳定性良好等特性,非常适合作为吸附材料。分子印迹聚合物和超分子化合物依靠主-客体特异性分子识别作用,能显著提高样品前处理方法的选择性。本文重点针对植物激素样品前处理中的SPE技术,综述了近5年来上述几类功能化吸附材料的最新应用进展,并对其发展趋势进行展望。

关键词: 吸附材料, 植物激素, 样品前处理, 固相萃取, 综述

Abstract:

Plant hormones (PHs) are of significance in plant growth, as they regulate the various processes related to plant growth, development, and resistance. Sensitive and precise quantitative analysis of PHs is a bottleneck in plant science research. Currently, liquid chromatography-tandem mass spectrometry is used for the accurate and efficient detection of PHs. Sample pretreatment is an indispensable step in the chromatography-mass spectrometry analysis of PHs because it directly affects the sensitivity and accuracy of subsequent detection methods. Among various pretreatment methods for PHs, solid phase extraction (SPE) is the most widely used. Various new types of SPE, such as dispersive SPE, magnetic SPE, and solid phase microextraction, have been developed by modifying the extraction cartridge. The choice of adsorption material is the key factor in the abovementioned SPE methods, which has a decisive effect on the extraction, purification, and enrichment effects of the target substance in the sample pretreatment process. Carbon-based materials, including carbon nanotubes, graphene, carbon and nitrogen compounds, as well as organic frameworks, including metal organic frameworks and covalent organic materials, are suitable adsorption materials because of their designable structure, large specific surface area, and good stability. Molecularly imprinted polymers and supramolecular compounds show specific molecular recognition based on host-guest interactions, which can significantly improve the selectivity of sample pretreatment methods. In this paper, SPE-related technology and the abovementioned types of functionalized adsorption materials in the pretreatment of PHs prevalent in the past five years have been reviewed. The related development trends are also summarized.

Key words: adsorption material, plant hormone, sample pretreatment, solid phase extraction (SPE), review

中图分类号:

O658

林舒婷, 丁青青, 张文敏, 张兰, 卢巧梅. 固相萃取吸附材料在植物激素样品前处理中的应用新进展[J]. 色谱, 2021, 39(12): 1281-1290.

LIN Shuting, DING Qingqing, ZHANG Wenmin, ZHANG Lan, LU Qiaomei. Novel adsorption material for solid phase extraction in sample pretreatment of plant hormones[J]. Chinese Journal of Chromatography, 2021, 39(12): 1281-1290.

图/表 3

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Type of plant hormones	Introduction	Common compounds and their abbreviations
Auxin (Aux)	Discovered in 1880, promote growth at low concentration while inhibit growth at high concentration.	indole acetic acid (IAA) 4-chloroindole acetic acid (4-Cl-IAA) indole butyric acid (IBA) indole propionic acid (IPA) naphthalene acetic acid (NAA) 2-naphthoxyacetic acid (2-NOA) 2,4-dichlorophenoxyacetic acid (2,4-D)
Gibberellins (GAs)	Discovered in 1934, promote cell elongation and germination, relieve seed dormancy, etc.	gibberellic acid (GA₃) gibberellin 1 (GA₁) gibberellin 4 (GA₄) gibberellin 7 (GA₇)
Cytokinins (CTKs)	Discovered in 1955, promote cell division and bud differentiation, delay senescence, etc.	zeatin (ZT) dihydrozeatin (DHZ) isopentenyl adenine (iP) zeatin riboside (ZR) kinetin (KT) 6-benzylaminopurine (BA)
Abscisic acid (ABA)	Discovered in 1963, promote dormancy, close stomata, increase stress resistance, etc.	abscisic acid
Ethylene (ETH)	Discovered in 1901, the only gaseous plant hormone, promote organ shedding, stomata closure and fruit ripening, etc.	ethylene
Brassinolides (BRs)	Discovered in 1979, promote cell elongation and division, enhance stress resistance, etc.	brassinolide (BL) 2,4-epibrassinolide (2,4-epiBL)
Strigolactones (SLs)	Discovered in 1966, promote the symbiosis of plants and soil microorganisms, etc.	strigolactone (SL) 5-deoxystrigol
Jasmonic acids (JAs)	Discovered in 1962, close stomata and enhance stress resistance.	jasmonic acid (JA) methyl jasmonate (MeJA)
Salicylic acid (SA)	Discovered in 1992, enhance stress resistance.	salicylic acid

Type of plant hormones	Introduction	Common compounds and their abbreviations
Auxin (Aux)	Discovered in 1880, promote growth at low concentration while inhibit growth at high concentration.	indole acetic acid (IAA) 4-chloroindole acetic acid (4-Cl-IAA) indole butyric acid (IBA) indole propionic acid (IPA) naphthalene acetic acid (NAA) 2-naphthoxyacetic acid (2-NOA) 2,4-dichlorophenoxyacetic acid (2,4-D)
Gibberellins (GAs)	Discovered in 1934, promote cell elongation and germination, relieve seed dormancy, etc.	gibberellic acid (GA₃) gibberellin 1 (GA₁) gibberellin 4 (GA₄) gibberellin 7 (GA₇)
Cytokinins (CTKs)	Discovered in 1955, promote cell division and bud differentiation, delay senescence, etc.	zeatin (ZT) dihydrozeatin (DHZ) isopentenyl adenine (iP) zeatin riboside (ZR) kinetin (KT) 6-benzylaminopurine (BA)
Abscisic acid (ABA)	Discovered in 1963, promote dormancy, close stomata, increase stress resistance, etc.	abscisic acid
Ethylene (ETH)	Discovered in 1901, the only gaseous plant hormone, promote organ shedding, stomata closure and fruit ripening, etc.	ethylene
Brassinolides (BRs)	Discovered in 1979, promote cell elongation and division, enhance stress resistance, etc.	brassinolide (BL) 2,4-epibrassinolide (2,4-epiBL)
Strigolactones (SLs)	Discovered in 1966, promote the symbiosis of plants and soil microorganisms, etc.	strigolactone (SL) 5-deoxystrigol
Jasmonic acids (JAs)	Discovered in 1962, close stomata and enhance stress resistance.	jasmonic acid (JA) methyl jasmonate (MeJA)
Salicylic acid (SA)	Discovered in 1992, enhance stress resistance.	salicylic acid

Adsorbent	Analytical method	Analyte	Detection limit		Sample	Reference
MWCNTs	SPE-HPLC	IBA, NAA	1.2-3.0	ng/mL	bean sprouts	[11]
CNTs-β-CD-HF	SPME-HPLC	NAA, 2-NOA	0.8-1.5	ng/g	tomato	[12]
CNTs-HF	EME-HPLC	NAA, 2-NOA	1.5-2.0	ng/g	tomato	[13]
N-doped CNTs-HF	SPME-HPLC	NAA, 2-NOA	1.0-1.5	ng/g	tomato	[14]
Ntim-GO/SiO₂	SPE-HPLC	SA	0.50	ng/mL	honey	[20]
Fe₃O₄/RGO@β-CD	MSPE-HPLC	NAA, 2-NOA	0.67	ng/g	tomato	[21]
Fe₃O₄@SiO₂/GO/ β-CD	MSPE-LC-MS/MS	NAA, 2,4-D, etc	0.04-0.28	ng/g	cucumber, tomato, sprouts, asparagus lettuce and cabbage	[23]
Fe₃O₄@SiO₂/GO/ β-CD/IL	MSPE-LC-MS/MS	Aux, CTKs	0.01-0.18	ng/g	cabbage, cucumber, tomato, eggplant and sprouts	[24]
C₁₈@GO@PDDA	SPME-HPLC	SA, 3-SA	1.8-2.8	ng/mL	aloe	[25]
GO/Ppy	PT-SPE-HPLC	IPA, IBA, NAA	1.2-1.7	ng/g	papaya	[26]
IL-TGO	PT-SPE-HPLC	IAA, NAA, 2,4-D	4.0-26	ng/g	bean sprouts	[27]
SiO₂@GO	dSPE-HPLC	Aux, ABA	30-50	ng/mL	arabidopsis, peach, cucumber, ginger and tomato	[29]
PEDOT-SG	SPME-HPLC	JA, MeJA	0.05-0.5	ng/mL	winter flower	[30]
GCB	dSPE-LC-MS/MS	Aux, CTKs, GAs, JAs, SA	0.02-31.09	fmol	rice	[33]
C₁₈, PSA, GCB	dSPE-LC-MS/MS	ABA, Aux, GAs, CTKs	<10	ng/g	Chinese medicine	[34]
PVPP-GCB	dSPE-LC-MS/MS	ABA, Aux, GAs	0.1-120.1	ng/g	tea	[35]
g-C₃N₄@SiO₂	SPE-HPLC	Aux, SA	1.9-5.7	ng/mL	coconut water	[37]
Co@Co₃O₄/OCN	MSPE-LC-MS/MS	IAA, IPA, IBA	0.2-4.0	pg/mL	perilla frutescens	[39]
CCFs	SPME-GC-MS	JA, IAA, ABA	0.04-0.17	ng/mL	tomato	[40]
CFs-IL	SPME-LC-MS/MS	Aux, ABA, GAs, CTKs, SA, JAs, BRs	1.3-55.7	pg/mL	tomato	[41]
Fe₃O₄@Ti₃C₂@β-CD	MSPE-UPLC-MS/MS	GAs, Aux, ABA, JA	2.18-45.39	pg/mL	oilseed	[42]

Adsorbent	Analytical method	Analyte	Detection limit		Sample	Reference
MWCNTs	SPE-HPLC	IBA, NAA	1.2-3.0	ng/mL	bean sprouts	[11]
CNTs-β-CD-HF	SPME-HPLC	NAA, 2-NOA	0.8-1.5	ng/g	tomato	[12]
CNTs-HF	EME-HPLC	NAA, 2-NOA	1.5-2.0	ng/g	tomato	[13]
N-doped CNTs-HF	SPME-HPLC	NAA, 2-NOA	1.0-1.5	ng/g	tomato	[14]
Ntim-GO/SiO₂	SPE-HPLC	SA	0.50	ng/mL	honey	[20]
Fe₃O₄/RGO@β-CD	MSPE-HPLC	NAA, 2-NOA	0.67	ng/g	tomato	[21]
Fe₃O₄@SiO₂/GO/ β-CD	MSPE-LC-MS/MS	NAA, 2,4-D, etc	0.04-0.28	ng/g	cucumber, tomato, sprouts, asparagus lettuce and cabbage	[23]
Fe₃O₄@SiO₂/GO/ β-CD/IL	MSPE-LC-MS/MS	Aux, CTKs	0.01-0.18	ng/g	cabbage, cucumber, tomato, eggplant and sprouts	[24]
C₁₈@GO@PDDA	SPME-HPLC	SA, 3-SA	1.8-2.8	ng/mL	aloe	[25]
GO/Ppy	PT-SPE-HPLC	IPA, IBA, NAA	1.2-1.7	ng/g	papaya	[26]
IL-TGO	PT-SPE-HPLC	IAA, NAA, 2,4-D	4.0-26	ng/g	bean sprouts	[27]
SiO₂@GO	dSPE-HPLC	Aux, ABA	30-50	ng/mL	arabidopsis, peach, cucumber, ginger and tomato	[29]
PEDOT-SG	SPME-HPLC	JA, MeJA	0.05-0.5	ng/mL	winter flower	[30]
GCB	dSPE-LC-MS/MS	Aux, CTKs, GAs, JAs, SA	0.02-31.09	fmol	rice	[33]
C₁₈, PSA, GCB	dSPE-LC-MS/MS	ABA, Aux, GAs, CTKs	<10	ng/g	Chinese medicine	[34]
PVPP-GCB	dSPE-LC-MS/MS	ABA, Aux, GAs	0.1-120.1	ng/g	tea	[35]
g-C₃N₄@SiO₂	SPE-HPLC	Aux, SA	1.9-5.7	ng/mL	coconut water	[37]
Co@Co₃O₄/OCN	MSPE-LC-MS/MS	IAA, IPA, IBA	0.2-4.0	pg/mL	perilla frutescens	[39]
CCFs	SPME-GC-MS	JA, IAA, ABA	0.04-0.17	ng/mL	tomato	[40]
CFs-IL	SPME-LC-MS/MS	Aux, ABA, GAs, CTKs, SA, JAs, BRs	1.3-55.7	pg/mL	tomato	[41]
Fe₃O₄@Ti₃C₂@β-CD	MSPE-UPLC-MS/MS	GAs, Aux, ABA, JA	2.18-45.39	pg/mL	oilseed	[42]

Adsorbent	Pretreatment	Analyte	Recovery/%		Sample	Reference
MOF-5	MSPE	GAs	71.8-	127.4	buckwheat seedling	[44]
ZIF-8/poly(MMA-EGDMA)	SBSE	ABA, Aux, SA	82.7-	111.0	apple, pear	[46]
ZIF-8@SiO₂	dSPE	Aux, CTKs	73.2-	89.6	navel orange	[47]
Fe₃O₄-MWCNTs-OH@poly-ZIF67	MSPE	NAA	92.4-	96.3	apple	[48]
Co@NC-MON-2NH₂	MSPE	SA, NAA, 1-NOA	77.9-	114.4	tomato, mung bean sprout, cucumber	[50]
UiO-67	dSPE	GA₃, Aux	89.3-	102.3	grapefruit, apple, pear	[51]
UiO-66/PAN	PT-SPE	Aux	88.3-	105.2	watermelon, mung bean sprouts	[52]
MSN@MIL-101(Fe)	dSPE	ABA, Aux	76.1-	113.0	mung bean sprouts	[53]
MOF-199/CNTs	SPME	ETH	86.8-	105.0	durian husk, wampee, blueberry, grape	[55]
CuTPA MOF	SPME	ETH	-		banana, avocado	[56]

固相萃取吸附材料在植物激素样品前处理中的应用新进展

Novel adsorption material for solid phase extraction in sample pretreatment of plant hormones

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