超交联多孔有机聚合物在柱固相萃取中的应用进展

doi:10.3724/SP.J.1123.2022.12003

摘要/Abstract

摘要：

超交联多孔有机聚合物(hypercrosslinked porous organic polymers, HCPs)是一类通过傅-克烷基化反应将芳香结构单元连接而制备得到的新型多孔材料,具有单体来源广泛、比表面积高、成本低廉、合成条件温和及易功能化等优点,广泛应用于气体储存、多相催化、色谱分离和有机污染物去除等领域。近年来,HCPs作为柱固相萃取吸附剂的研究较多,展现出巨大的应用潜力。基于高比表面积、优异的吸附性能、多样化的化学结构和易于化学改性等优点,HCPs材料被成功应用于不同样品基质中多种类型分析物的萃取并表现出优异的萃取性能。根据HCPs的骨架化学结构、目标分析物的性质及两者间的作用机理,我们将HCPs分为疏水型、亲水型、离子型3类,介绍了各种HCPs的特点、合成方法和在柱固相萃取中的应用。基于HCPs与分析物之间的疏水、π-π、亲水、氢键、离子交换等多种相互作用机理,HCPs萃取材料能够高效萃取和选择性富集不同种类的目标分析物,如苯脲类除草剂、氯酚类化合物、硝基咪唑、四环素、酸碱性药物等。将新型HCPs萃取与色谱、质谱等现代分析技术结合的方法已广泛应用于环境监测、食品安全和生化分析等领域。本文对HCPs在填充柱固相萃取中的应用进行了全面综述,并对其未来发展做出了展望。

关键词: 超交联多孔有机聚合物, 柱固相萃取, 吸附剂, 吸附机理

Abstract:

Hypercrosslinked porous organic polymers (HCPs), a novel type of porous materials synthesized via the Friedel-Crafts reaction, are widely used in gas storage, heterogeneous catalysis, chromatographic separation, and organic pollutant capture. HCPs have the advantages of a wide monomer source, low cost, mild synthesis conditions, and easy functionalization. In recent years, HCPs have shown great application potential in solid phase extraction. Given their high specific surface area, excellent adsorption properties, diverse chemical structures, and easy chemical modification, HCPs have been successfully applied to the extraction of different types of analytes with efficient extraction performance. Based on the chemical structure of HCPs, their target analytes, and the adsorption mechanism, HCPs can be classified as hydrophobic, hydrophilic, and ionic species. Hydrophobic HCPs are usually constructed as extended conjugated structures by overcrosslinking aromatic compounds as monomers. Common monomers include ferrocene, triphenylamine, triphenylphosphine, etc. This type of HCPs shows good adsorption effects on nonpolar analytes such as benzuron herbicides and phthalates through strong π-π and hydrophobic interactions. Hydrophilic HCPs are prepared by introducing polar monomers or crosslinking agents, or by modifying polar functional groups. This type of adsorbent is commonly used to extract polar analytes such as nitroimidazole, chlorophenol, tetracycline, etc. In addition to hydrophobic forces, polar interactions, such as hydrogen-bonding and dipole-dipole interactions, also occur between the adsorbent and analyte. Ionic HCPs are mixed-mode solid phase extraction materials formed by introducing ionic functional groups into the polymer. Mixed-mode adsorbents usually have a dual reversed-phase/ion-exchange retention mechanism, which helps control the retention behavior of the adsorbent by adjusting the elution strength of the eluting solvent. In addition, the extraction mode can be switched by controlling the pH of the sample solution and eluting solvent. In this manner, matrix interferences can be removed while the target analytes are enriched. Ionic HCPs present a unique advantage in the extraction of acid-base drugs in water. The combination of new HCP extraction materials with modern analytical techniques, such as chromatography and mass spectrometry, has been widely used in environmental monitoring, food safety, and biochemical analyses. In this review, the characteristics and synthesis methods of HCPs are briefly introduced, and the application progress of different types of HCPs in cartridge-based solid phase extraction is described. Finally, the future outlook of HCP applications is discussed.

Key words: hypercrosslinked porous organic polymers (HCPs), cartridge-based solid phase extraction, adsorbents, adsorption mechanism

中图分类号:

O658

秦童童, 高莉, 赵文杰. 超交联多孔有机聚合物在柱固相萃取中的应用进展[J]. 色谱, 2023, 41(7): 554-561.

QIN Tongtong, GAO Li, ZHAO Wenjie. Application progress of hypercrosslinked porous organic polymers in cartridge-based solid phase extraction[J]. Chinese Journal of Chromatography, 2023, 41(7): 554-561.

图/表 4

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Sorbent	Monomer	Synthesized method	Analytes	Mechanism	Sample	Ref.
HCPs	styrene	post-crosslinking	sulfanilamides	π-π, hydrophobic	river water	[19]
Fc-NOP	ferrocene	one-step polycon- densation	phenylurea herbicides	π-π, hydrophobic	tap water, black tea drinks, peach juice	[20]
PPTPA	triphenylamine	one-step polycon- densation	phenylurea herbicides	π-π, hydrophobic, hydrogen bonding	water, milk, tomato juice	[21]
Ph-PPh₃-KAP	PPh₃, benzene	external crosslinking	phenylurea pesticides	π-π, hydrogen bonding	lake water, tomato, cucumber	[22]
Py-DMB-HCP	pyrrole	external crosslinking	phenylurea pesticides	π-π, hydrophobic, hydrogen bonding	soybean milk, tomato	[23]
HCTPA	triphenylamine	external crosslinking	phenylurea pesticides	π-π, hydrophobic, hydrogen bonding	watermelon, tomato, cucumber	[24]
PTPA	triphenylamine	external crosslinking	chlorophenols	π-π, hydrophobic, hydrogen bonding	peach juice, green tea beverage, tomato	[25]
HCP-TPS	triphenylsilane	one-step polycon- densation	chlorophenols	π-π, hydrophobic, hydrogen bonding	water, honey, white peach beverage	[26]
HCP-Kae1-24h	kaempferol	one-step polycon- densation	nitroimidazoles	weak π-π, hydropho- bic, hydrogen bonding	water, honey, fish meat	[28]
API-HCP	apigenin	one-step polycon- densation	chlorophenols	hydrogen bonding, halogen bonding, π-π stacking	water, honey	[29]
HCP@Tyr	TPB, L-Tyr	external crosslinking	nitroimidazoles	π-π, hydrogen bond- ing, hydrophilic	honey, chicken muscle	[30]
PBA-HCP	PBA	external crosslinking	chlorophenols	hydrophilic, hydrogen bonding	water, honey-pomelo beverage	[31]
MPD-HCP	MPD	external crosslinking	nitroimidazoles	electrostatic, hydrogen bonding, hydrophilic	water, peach juice, honey tea, honey	[32]
CTP_CC-TP	terphenyl, cyanuric chloride	one-step polycon- densation	tetracycline	hydrophilic, hydropho- bic, hydrogen bonding	bovine milk, egg, chicken liver	[33]
HXLPP	VBC, DVB	post-crosslinking	polar pollutants	hydrophilic, hydrogen bonding, polar	ultrapure, mineral, tap and Ebre river water	[34]
HXLGp	2% DVB, 98% VBC	post-crosslinking	polar pollutants	hydrophilic, hydrogen bonding, polar	tap, river water	[35]
HXLPP-WAX-EDA HXLPP-WAX- piperazine	75%VBC, 25%DVB	post-crosslinking	acidic com- pounds	reversed-phase, weak anion exchange	Ebre river water, efflu- ent waste water	[36]
HXLPP-WAX-EDA	75% VBC, 25% DVB	post-crosslinking	acidic com- pounds	reversed-phase, weak anion exchange	ultrapure, river, effluent sewage water	[37]
HXLPP-WAX	VBC, DVB	post-crosslinking	homovanilic acid	reversed-phase, weak anion exchange	human urine	[38]
HXLPP-SAX_a, HXLPP-SAX_b	75% VBC, 25% DVB	post-crosslinking	acidic pharma- ceuticals	reversed-phase, strong anion exchange	Ebre river water, sew- age water	[39]
HXLPP-SAX-N(CH₃)	VBC, DVB	post-crosslinking	fluoroquinolone drugs	reversed-phase, strong anion exchange	milk	[40]
HXLPP-WCX-MAA	10% MAA, 50% VBC and 40% DVB	post-crosslinking	basic pharma- ceuticals	reversed-phase, weak cation exchange	Ebre river water, waste water	[41]
HXLPP-SCX	VBC, DVB	post-crosslinking	hypoxanthine, xanthine and inosine	reversed-phase, strong cation exchange	serum	[42]
HXLPP-SAX/WCX, HXLPP-WAX/SCX	poly(divinyl- benzene-co-vinyl- benzylchloride)	post-crosslinking	acidic and basic drugs	reversed-phase, ion exchange	river water, effluent waste water	[43]

Sorbent	Monomer	Synthesized method	Analytes	Mechanism	Sample	Ref.
HCPs	styrene	post-crosslinking	sulfanilamides	π-π, hydrophobic	river water	[19]
Fc-NOP	ferrocene	one-step polycon- densation	phenylurea herbicides	π-π, hydrophobic	tap water, black tea drinks, peach juice	[20]
PPTPA	triphenylamine	one-step polycon- densation	phenylurea herbicides	π-π, hydrophobic, hydrogen bonding	water, milk, tomato juice	[21]
Ph-PPh₃-KAP	PPh₃, benzene	external crosslinking	phenylurea pesticides	π-π, hydrogen bonding	lake water, tomato, cucumber	[22]
Py-DMB-HCP	pyrrole	external crosslinking	phenylurea pesticides	π-π, hydrophobic, hydrogen bonding	soybean milk, tomato	[23]
HCTPA	triphenylamine	external crosslinking	phenylurea pesticides	π-π, hydrophobic, hydrogen bonding	watermelon, tomato, cucumber	[24]
PTPA	triphenylamine	external crosslinking	chlorophenols	π-π, hydrophobic, hydrogen bonding	peach juice, green tea beverage, tomato	[25]
HCP-TPS	triphenylsilane	one-step polycon- densation	chlorophenols	π-π, hydrophobic, hydrogen bonding	water, honey, white peach beverage	[26]
HCP-Kae1-24h	kaempferol	one-step polycon- densation	nitroimidazoles	weak π-π, hydropho- bic, hydrogen bonding	water, honey, fish meat	[28]
API-HCP	apigenin	one-step polycon- densation	chlorophenols	hydrogen bonding, halogen bonding, π-π stacking	water, honey	[29]
HCP@Tyr	TPB, L-Tyr	external crosslinking	nitroimidazoles	π-π, hydrogen bond- ing, hydrophilic	honey, chicken muscle	[30]
PBA-HCP	PBA	external crosslinking	chlorophenols	hydrophilic, hydrogen bonding	water, honey-pomelo beverage	[31]
MPD-HCP	MPD	external crosslinking	nitroimidazoles	electrostatic, hydrogen bonding, hydrophilic	water, peach juice, honey tea, honey	[32]
CTP_CC-TP	terphenyl, cyanuric chloride	one-step polycon- densation	tetracycline	hydrophilic, hydropho- bic, hydrogen bonding	bovine milk, egg, chicken liver	[33]
HXLPP	VBC, DVB	post-crosslinking	polar pollutants	hydrophilic, hydrogen bonding, polar	ultrapure, mineral, tap and Ebre river water	[34]
HXLGp	2% DVB, 98% VBC	post-crosslinking	polar pollutants	hydrophilic, hydrogen bonding, polar	tap, river water	[35]
HXLPP-WAX-EDA HXLPP-WAX- piperazine	75%VBC, 25%DVB	post-crosslinking	acidic com- pounds	reversed-phase, weak anion exchange	Ebre river water, efflu- ent waste water	[36]
HXLPP-WAX-EDA	75% VBC, 25% DVB	post-crosslinking	acidic com- pounds	reversed-phase, weak anion exchange	ultrapure, river, effluent sewage water	[37]
HXLPP-WAX	VBC, DVB	post-crosslinking	homovanilic acid	reversed-phase, weak anion exchange	human urine	[38]
HXLPP-SAX_a, HXLPP-SAX_b	75% VBC, 25% DVB	post-crosslinking	acidic pharma- ceuticals	reversed-phase, strong anion exchange	Ebre river water, sew- age water	[39]
HXLPP-SAX-N(CH₃)	VBC, DVB	post-crosslinking	fluoroquinolone drugs	reversed-phase, strong anion exchange	milk	[40]
HXLPP-WCX-MAA	10% MAA, 50% VBC and 40% DVB	post-crosslinking	basic pharma- ceuticals	reversed-phase, weak cation exchange	Ebre river water, waste water	[41]
HXLPP-SCX	VBC, DVB	post-crosslinking	hypoxanthine, xanthine and inosine	reversed-phase, strong cation exchange	serum	[42]
HXLPP-SAX/WCX, HXLPP-WAX/SCX	poly(divinyl- benzene-co-vinyl- benzylchloride)	post-crosslinking	acidic and basic drugs	reversed-phase, ion exchange	river water, effluent waste water	[43]