色谱 ›› 2023, Vol. 41 ›› Issue (4): 289-301.DOI: 10.3724/SP.J.1123.2022.06001
叶翰章1, 刘婷婷1,2, 丁永立1, 顾婧婧1, 李宇浩1, 王琪1, 张占恩1,*(), 王学东1,*(
)
收稿日期:
2022-06-03
出版日期:
2023-04-08
发布日期:
2023-04-03
通讯作者:
*E-mail: zhanenzhang@126.com(张占恩); E-mail: zjuwxd@163.com(王学东).
基金资助:
YE Hanzhang1, LIU Tingting1,2, DING Yongli1, GU Jingjing1, LI Yuhao1, WANG Qi1, ZHANG Zhan’en1,*(), WANG Xuedong1,*(
)
Received:
2022-06-03
Online:
2023-04-08
Published:
2023-04-03
Supported by:
摘要:
泡腾辅助微萃取(EAM)技术是一种利用CO2供体和H+供体反应产生CO2气泡促进萃取剂快速分散、增大与目标物的接触面积,以实现高效萃取的新型样品预处理手段。该技术具有分散速率快、萃取效率高、使用成本低、应用范围广等优点。得益于萃取剂的快速发展,泡腾辅助微萃取方法的构建和应用范围研究日趋完善和多样,已广泛用于环境、食品、生物等样品的前处理领域。该前处理技术结合各类检测仪器构建新型快速的检测方法,成功实现了重金属离子、农药、内分泌干扰物、抗生素等污染物的检测。在EAM技术的构建中,常考查泡腾片剂的组成、溶液pH、萃取温度、萃取剂种类、萃取剂添加量、洗脱剂种类、洗脱剂体积、洗脱时间、循环使用次数等因素对方法的影响,重点依据线性范围、相关系数、富集因子、检出限、定量限等参数对方法进行评判,最后结合各类仪器检测方法,实现在实际样品检测中的应用。该文从EAM技术常用的萃取剂方面入手,综述了基于纳米材料、离子液体等新兴萃取剂的EAM方法的构建,以及与液相色谱、气相色谱、原子吸收光谱或质谱等大型仪器联用,用于复杂基质中有害物质检测的研究与应用进展,分析了该技术在使用过程中存在的问题,展望了其未来在微萃取领域中的发展趋势。
中图分类号:
叶翰章, 刘婷婷, 丁永立, 顾婧婧, 李宇浩, 王琪, 张占恩, 王学东. 泡腾辅助微萃取技术的开发与应用研究进展[J]. 色谱, 2023, 41(4): 289-301.
YE Hanzhang, LIU Tingting, DING Yongli, GU Jingjing, LI Yuhao, WANG Qi, ZHANG Zhan’en, WANG Xuedong. Recent advances in the development and application of effervescence-assisted microextraction techniques[J]. Chinese Journal of Chromatography, 2023, 41(4): 289-301.
图1 (A)泡腾辅助磁固相微萃取技术流程图和(B)实际泡腾片图[34]
Fig. 1 (A) Schematic diagram of the effervescence-assisted magnetic solid-phase microextraction process and (B) photographic images of the effervescent tables[34]
图2 (A)泡腾辅助分散液液微萃取技术流程图[32]与(B)实际泡腾辅助液液微萃取流程图[35]
Fig. 2 (A) Schematic diagram of the effervescence- assisted dispersive liquid-liquid microextraction process[32], and (B) photographic images of the effervescence-assisted dispersive liquid-liquid microextraction process[35]
Effervescent agents | Extractant | Analytes | Samples | Sample preparation | Measurement | Extraction time | Recoveries/ % | Ref. | |
---|---|---|---|---|---|---|---|---|---|
CO2 source | H+ source | ||||||||
Na2CO3 | NaH2PO4 | MWCNTs | triazines | water | MWCNT | UPLC-UV | 3 min | 77-101 | [ |
Na2CO3 | NaH2PO4 | NiFe2O4 MNPs | heavy metals | seafood extracts | MNET-DSPM | ICP-MS | < 3 min | 73.4-99.3 | [ |
Na2CO3 | NaH2PO4 | GMWCNTs-COOH | natural antioxi- dants | hawthorn herb | ENMAM | UHPLC-ECD | 10 min | 15-96 | [ |
Na2CO3 | citric acid | nano-(Fe3O4/CS-Se)2 | heavy metals | sausage extracts and water | EA-DM-μSPE | μS-FAAs | 4.5 min | 95.6-104.1 | [ |
NaHCO3 | NaH2PO4 | sulfonate PS-DVB- CNT | alkaloids and flavonoids | biological samples | EPT-SPME | UHPLC-UV | 1.2 min | 90.05-99.85 | [ |
Na2CO3 | citric acid | Fe3O4@SiO2@N3 MNPs | antidepressant drugs | urine and pharma- ceutical wastewater | EA-DM-mSPE | / | < 6 min | ≥70 | [ |
Na2CO3 | NaH2PO4 | core-shell mag- netic COF | endocrine dis- ruptors | water, beverages and biosamples | MNER-EM | HPLC-FLD | 5 min | 83.4-106.2 | [ |
Na2CO3 | NaH2PO4 | mesoporous hy- brid materials (PCMA-60) | tanshinones | root extracts (CDDP, DT) | DMSPE | UPLC | 30 min | 90-101 | [ |
Na2CO3 | NaH2PO4 | β-cyclodextrin/attapulgite compos- ite | pyrethroids | water | EAIS-DSPE | HPLC-UV | - | 76.8-86.5 | [ |
Na2CO3 | tartaric acid | mETDSE/Ni@ N-GrTs | trace bisphe- nols | milk | mETDSE | HPLC-FLD | 6.3 min | 83.6-105.1 | [ |
Na2CO3 | NaH2PO4 | ATP/PPY/Fe3O4 | pyrethroids | honey | MEA-DSPE | HPLC-DAD | 5 min | 81.42-106.73 | [ |
NaHCO3 | citric acid | Fe3O4@porous activated carbon | phenolic endo- crine disrup- ting chemicals | environmental water | META-DES- DLLME | HPLC | 30 s | 81.0-94.7 | [ |
Na2CO3 | tartaric acid | mNH2-MIL-101 (Al)@β-CD@GO | PAHs and BPs | roasted meat | ENCG | HPLC-FLD | 40 s | 86.9-103.9 | [ |
Na2CO3 | tartaric acid | Ni@N-CNTs | estrogens | milk | MSPE | HPLC-FLD | 3 min | 85.2-102.9 | [ |
Na2CO3 | citric acid | graphene oxide modified with dopamine | metal ions | sausages and water | EA-DM-mSPE | ASS | 3 min | 95.5-98.0 | [ |
表1 纳米材料基-EAM技术在目标物分析检测中的应用
Table 1 Nanomaterial-based effervescence-assisted microextraction (EAM) for sample preparation prior to target detection and analysis
Effervescent agents | Extractant | Analytes | Samples | Sample preparation | Measurement | Extraction time | Recoveries/ % | Ref. | |
---|---|---|---|---|---|---|---|---|---|
CO2 source | H+ source | ||||||||
Na2CO3 | NaH2PO4 | MWCNTs | triazines | water | MWCNT | UPLC-UV | 3 min | 77-101 | [ |
Na2CO3 | NaH2PO4 | NiFe2O4 MNPs | heavy metals | seafood extracts | MNET-DSPM | ICP-MS | < 3 min | 73.4-99.3 | [ |
Na2CO3 | NaH2PO4 | GMWCNTs-COOH | natural antioxi- dants | hawthorn herb | ENMAM | UHPLC-ECD | 10 min | 15-96 | [ |
Na2CO3 | citric acid | nano-(Fe3O4/CS-Se)2 | heavy metals | sausage extracts and water | EA-DM-μSPE | μS-FAAs | 4.5 min | 95.6-104.1 | [ |
NaHCO3 | NaH2PO4 | sulfonate PS-DVB- CNT | alkaloids and flavonoids | biological samples | EPT-SPME | UHPLC-UV | 1.2 min | 90.05-99.85 | [ |
Na2CO3 | citric acid | Fe3O4@SiO2@N3 MNPs | antidepressant drugs | urine and pharma- ceutical wastewater | EA-DM-mSPE | / | < 6 min | ≥70 | [ |
Na2CO3 | NaH2PO4 | core-shell mag- netic COF | endocrine dis- ruptors | water, beverages and biosamples | MNER-EM | HPLC-FLD | 5 min | 83.4-106.2 | [ |
Na2CO3 | NaH2PO4 | mesoporous hy- brid materials (PCMA-60) | tanshinones | root extracts (CDDP, DT) | DMSPE | UPLC | 30 min | 90-101 | [ |
Na2CO3 | NaH2PO4 | β-cyclodextrin/attapulgite compos- ite | pyrethroids | water | EAIS-DSPE | HPLC-UV | - | 76.8-86.5 | [ |
Na2CO3 | tartaric acid | mETDSE/Ni@ N-GrTs | trace bisphe- nols | milk | mETDSE | HPLC-FLD | 6.3 min | 83.6-105.1 | [ |
Na2CO3 | NaH2PO4 | ATP/PPY/Fe3O4 | pyrethroids | honey | MEA-DSPE | HPLC-DAD | 5 min | 81.42-106.73 | [ |
NaHCO3 | citric acid | Fe3O4@porous activated carbon | phenolic endo- crine disrup- ting chemicals | environmental water | META-DES- DLLME | HPLC | 30 s | 81.0-94.7 | [ |
Na2CO3 | tartaric acid | mNH2-MIL-101 (Al)@β-CD@GO | PAHs and BPs | roasted meat | ENCG | HPLC-FLD | 40 s | 86.9-103.9 | [ |
Na2CO3 | tartaric acid | Ni@N-CNTs | estrogens | milk | MSPE | HPLC-FLD | 3 min | 85.2-102.9 | [ |
Na2CO3 | citric acid | graphene oxide modified with dopamine | metal ions | sausages and water | EA-DM-mSPE | ASS | 3 min | 95.5-98.0 | [ |
Effervescent agents | Extractant | ILs type | Analytes | Samples | Sample preparation | Measurement | Extraction time/min | Recoveries/ % | Ref. | |
---|---|---|---|---|---|---|---|---|---|---|
CO2 source | H+ source | |||||||||
Na2CO3 | TTA | [C6MIM]PF6 | [C6MIM]BF4 | endogenous steroids | serum and urine | IS-META-ILDM | HPLC-UV | 3 | 90.0-118.5 | [ |
Na2CO3 | NaH2PO4 | IL-M-β-CD/ATP | [OMIM]NTF2 | fungicides | honey/juice | EA-DSPE | HPLC-DAD | 3 | 77.0-94.3 | [ |
Na2CO3 | HCl | [C6MIM]PF6 | [C6MIM]PF6 | pyrethroids | milk | MET-ILM | GC-ECD | 2 | 78.3-101.8 | [ |
Na2CO3 | NaH2PO4 | [C4MIM][FeCl4] | [C4MIM][FeCl4] | As | vegetable | ETA-MILs-ME | GFAAS | <1 | 97.9-105.8 | [ |
Na2CO3 | NaH2PO4 | IL@SiO2@Fe3O4 | [BMIM]PF6 | beta block- ers | plasma | DSPE-IL@MNP-EP | LC-MS | 75-91 | [ | |
Na2CO3 | NaH2PO4 | [C4MIM]PF6 | [C4MIM]PF6 | PBDEs | water/milk/ serum | META-IL-DLLME | HPLC-DAD | <1 | 77.3-106.7 | [ |
NaHCO3 | TTA | [BMIM]PF6 | [BMIM]PF6 | BUIs | fruit juice/ vegetable | EA-DLLME | HPLC-DAD | 6 | 74-93 | [ |
Na2CO3 | NaH2PO4 | [C6MIM]PF6 | [C6MIM]PF6 | Se | beverage/food | MEA-IL-DLLME | GFAAS | 92.0-108.1 | [ | |
Na2CO3 | NaH2PO4 | [C6MIM]PF6 | [C6MIM]PF6 | PAHs | milk | NIE-DSM | HPLC-FLD | 3 | 74.1-101.6 | [ |
NaHCO3 | acidic TSIL | [C4MIM][HSO4] | [C4MIM][HSO4] | triazine her- bicides | tea beverage | EA-DLLME | HPLC-UV | 2 | 77.1-114.7 | [ |
Na2CO3 | starch | [HMIM]NTF@ NiFe2O4 | [HMIM]NTF | phthalate esters | milks | MMIL-EFM | HPLC-UV | 7 | 94.8-105.6 | [ |
Na2CO3 | LPIL | tetradecyl(tri- hexyl) phospho- nium chloride | CYPHOS IL 101 | PAHs | edible oils | EM-LPSH | HPLC-FLD | 5 | 80.1-103.3 | [ |
Na2CO3 | NaH2PO4 | [HMIM]NTF2 | [HMIM]NTF2 | fungicide | water | META-IL-DLLME | HPLC-DAD | 1 | 70.7-105 | [ |
Na2CO3 | NaH2PO4 | [C4(MIM)2] [N(CN)2] | [C4(MIM)2]Br2 | PAHs | meat | EIDLM | HPLC-FLD | 4 | 82.3-104.7 | [ |
Na2CO3 | NaH2PO4 | IL-TiO2 nanofluid | [OMIM]NTF2 | acaricide | honey and tea | EA-DLLME | HPLC-DAD | 5 | 64.08-92.65 | [ |
表2 离子液体基-EAM技术在目标物分析检测中的应用
Table 2 Ionic liquid-based effervescence-assisted microextraction for sample preparation prior to target detection and analysis
Effervescent agents | Extractant | ILs type | Analytes | Samples | Sample preparation | Measurement | Extraction time/min | Recoveries/ % | Ref. | |
---|---|---|---|---|---|---|---|---|---|---|
CO2 source | H+ source | |||||||||
Na2CO3 | TTA | [C6MIM]PF6 | [C6MIM]BF4 | endogenous steroids | serum and urine | IS-META-ILDM | HPLC-UV | 3 | 90.0-118.5 | [ |
Na2CO3 | NaH2PO4 | IL-M-β-CD/ATP | [OMIM]NTF2 | fungicides | honey/juice | EA-DSPE | HPLC-DAD | 3 | 77.0-94.3 | [ |
Na2CO3 | HCl | [C6MIM]PF6 | [C6MIM]PF6 | pyrethroids | milk | MET-ILM | GC-ECD | 2 | 78.3-101.8 | [ |
Na2CO3 | NaH2PO4 | [C4MIM][FeCl4] | [C4MIM][FeCl4] | As | vegetable | ETA-MILs-ME | GFAAS | <1 | 97.9-105.8 | [ |
Na2CO3 | NaH2PO4 | IL@SiO2@Fe3O4 | [BMIM]PF6 | beta block- ers | plasma | DSPE-IL@MNP-EP | LC-MS | 75-91 | [ | |
Na2CO3 | NaH2PO4 | [C4MIM]PF6 | [C4MIM]PF6 | PBDEs | water/milk/ serum | META-IL-DLLME | HPLC-DAD | <1 | 77.3-106.7 | [ |
NaHCO3 | TTA | [BMIM]PF6 | [BMIM]PF6 | BUIs | fruit juice/ vegetable | EA-DLLME | HPLC-DAD | 6 | 74-93 | [ |
Na2CO3 | NaH2PO4 | [C6MIM]PF6 | [C6MIM]PF6 | Se | beverage/food | MEA-IL-DLLME | GFAAS | 92.0-108.1 | [ | |
Na2CO3 | NaH2PO4 | [C6MIM]PF6 | [C6MIM]PF6 | PAHs | milk | NIE-DSM | HPLC-FLD | 3 | 74.1-101.6 | [ |
NaHCO3 | acidic TSIL | [C4MIM][HSO4] | [C4MIM][HSO4] | triazine her- bicides | tea beverage | EA-DLLME | HPLC-UV | 2 | 77.1-114.7 | [ |
Na2CO3 | starch | [HMIM]NTF@ NiFe2O4 | [HMIM]NTF | phthalate esters | milks | MMIL-EFM | HPLC-UV | 7 | 94.8-105.6 | [ |
Na2CO3 | LPIL | tetradecyl(tri- hexyl) phospho- nium chloride | CYPHOS IL 101 | PAHs | edible oils | EM-LPSH | HPLC-FLD | 5 | 80.1-103.3 | [ |
Na2CO3 | NaH2PO4 | [HMIM]NTF2 | [HMIM]NTF2 | fungicide | water | META-IL-DLLME | HPLC-DAD | 1 | 70.7-105 | [ |
Na2CO3 | NaH2PO4 | [C4(MIM)2] [N(CN)2] | [C4(MIM)2]Br2 | PAHs | meat | EIDLM | HPLC-FLD | 4 | 82.3-104.7 | [ |
Na2CO3 | NaH2PO4 | IL-TiO2 nanofluid | [OMIM]NTF2 | acaricide | honey and tea | EA-DLLME | HPLC-DAD | 5 | 64.08-92.65 | [ |
Effervescent agents | Extractant | Analytes | Samples | Sample preparation | Measurement | Extraction time/min | Recoveries/ % | Ref. | |
---|---|---|---|---|---|---|---|---|---|
CO2 source | H+ source | ||||||||
Na2CO3 | citric acid | 1-undecanol | triazine herbicides and triazole fungi- cides | water | EA-DLLME-CFO | LC-MS | 3 | 72.4-101.5 | [ |
NaHCO3 | NaH2PO4 | sodium dodecyl sulfate | coumarins | cortex fraxini | EA-MSPD | UHPLC | 5 | 91.37-100.29 | [ |
Na2CO3 | H2SO4 | hexanoic acid | toxic azo dyes | food | CO2-EA-EME-SS | HPLC | 1 | 86.6-104.5 | [ |
Na2CO3 | fatty acid | nonionic acid | antibiotics | seawater, sedi- ment, and seafood | EA-SFAM-SFO | HPLC-UV | 5 | 82.2-116.7 | [ |
NaHCO3 | CH3COOH | hydrophobic deep eutectic solvent | colorants | food | EA-DLLME-DES | UV-Vis spec- troscopy | 10 | 97.9-101.7 | [ |
NaHCO3 | citric acid | octanoic acid | endocrine disrup- tor | bottled beverages | ETA-SHS-ME-SFO | HPLC | 1.5 | 71.7-98.1 | [ |
NaHCO3 | citric acid | Fe3O4 | triazine herbicides | water | META-SHS-LPME | HPLC | 5 | 81.4-96.7 | [ |
Na2CO3 | formic acid | hydrophobic deep eutectic solvent | nonsteroidal anti- inflammatory drugs | liver | EA-DLLME | HPLC-MS/MS | 5 | 92-108 | [ |
NaHCO3 | citric acid | hydrophobic deep eutectic solvent | strobilurin fungi- cides | water, juice, wine, and vinegar | ETA-ME-SDES | HPLC | 5 | 77.4-106.9 | [ |
表3 其他吸附剂基-EAM技术在目标物分析检测中的应用
Table 3 Other sorbent-based effervescence-assisted microextraction for sample preparation prior to target detection and analysis
Effervescent agents | Extractant | Analytes | Samples | Sample preparation | Measurement | Extraction time/min | Recoveries/ % | Ref. | |
---|---|---|---|---|---|---|---|---|---|
CO2 source | H+ source | ||||||||
Na2CO3 | citric acid | 1-undecanol | triazine herbicides and triazole fungi- cides | water | EA-DLLME-CFO | LC-MS | 3 | 72.4-101.5 | [ |
NaHCO3 | NaH2PO4 | sodium dodecyl sulfate | coumarins | cortex fraxini | EA-MSPD | UHPLC | 5 | 91.37-100.29 | [ |
Na2CO3 | H2SO4 | hexanoic acid | toxic azo dyes | food | CO2-EA-EME-SS | HPLC | 1 | 86.6-104.5 | [ |
Na2CO3 | fatty acid | nonionic acid | antibiotics | seawater, sedi- ment, and seafood | EA-SFAM-SFO | HPLC-UV | 5 | 82.2-116.7 | [ |
NaHCO3 | CH3COOH | hydrophobic deep eutectic solvent | colorants | food | EA-DLLME-DES | UV-Vis spec- troscopy | 10 | 97.9-101.7 | [ |
NaHCO3 | citric acid | octanoic acid | endocrine disrup- tor | bottled beverages | ETA-SHS-ME-SFO | HPLC | 1.5 | 71.7-98.1 | [ |
NaHCO3 | citric acid | Fe3O4 | triazine herbicides | water | META-SHS-LPME | HPLC | 5 | 81.4-96.7 | [ |
Na2CO3 | formic acid | hydrophobic deep eutectic solvent | nonsteroidal anti- inflammatory drugs | liver | EA-DLLME | HPLC-MS/MS | 5 | 92-108 | [ |
NaHCO3 | citric acid | hydrophobic deep eutectic solvent | strobilurin fungi- cides | water, juice, wine, and vinegar | ETA-ME-SDES | HPLC | 5 | 77.4-106.9 | [ |
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