Research progress in material preparation and application of magnetism-enhanced in-tube solid-phase microextraction

doi:10.3724/SP.J.1123.2024.05030

Abstract

Abstract:

Selecting a suitable sample preparation method is a significant step prior to chromatographic separation and detection. Directly analyzing samples instrumentally is difficult owing to the complexity of the sample matrix and the trace concentration of analytes. Most sample preparation methods have disadvantages， including complicated operating procedures， the use of large amounts of organic solvent， and ease of analyte loss during multistep processes； consequently， they do not meet the high analytical sample detection requirements of modern industry. The development of simple， environmentally friendly， efficient， and rapid preparation methods is a continuing frontier research area in the analytical chemistry field. Among the many available sample preparation techniques， in-tube solid-phase microextraction （IT-SPME） is receiving extensive attention. IT-SPME enriches the target analytes by extracting them to the inner surface of the capillary tube， and has been applied to extract various analytes in the environmental and food fields. IT-SPME is advantageous because it consumes low amounts of organic solvent and capillaries are mechanical stable； consequently， IT-SPME is a promising sample preparation technique. Magnetic field has been introduced to the IT-SPME system to further improve extraction efficiency and selectivity， leading to the development of magnetism-enhanced in-tube solid-phase microextraction （ME-IT-SPME） as a new technology. ME-IT-SPME uses magnetic field to separate and enrich targets， with different magnetic-field strengths applied to the extraction column during adsorption and elution. Diamagnetic substances in a paramagnetic medium tend to concentrate in regions where the magnetic field is weak when an external magnetic field is applied. Target analytes are detected chromatographically following elution. Conditions are optimized and an analytical method is established and used to detect targets in actual samples， leading to improved extraction sensitivity and precision compared to those obtained using IT-SPME， including shorter analysis time and superior extraction efficiency. This paper reviews the applications of ME-IT-SPME technology in combination with various analytical instruments since its inception in 2012， and analyzes its analysis and detection advantages. Based on hydrophobic interactions， hydrogen bonding， π-π and polarity interactions， coordination， and other extraction mechanisms with analytes， ME-IT-SPME uses innovative functional extraction materials， including nanomaterials， monolithic materials， and magnetic hybrid materials， all of which have high surface areas and numerous adsorption sites. Capillary microextraction columns are prepared using open-tubular capillary， particle-filling capillary， or monolithic capillaries. Diverse analytes are detected when ME-IT-SPME is combined with chromatograph， including organic pesticide residues， heavy-metal ions， herbicides， preservatives， and drug molecules. ME-IT-SPME technology is widely used in the environmental-analysis， food-analysis， and biomedical fields. Future， ME-IT-SPME technological developments should include：（1） focus on the reusability and stability of the magnetic extraction material；（2） discovering new extraction materials that are highly enriching and selective in order to analyze a greater variety of targets；（3） further innovating ME-IT-SPME technology by combining it with other more-sensitive analytical methods and considering its use in other fields；（4） connecting different capillaries to simultaneously enrich a variety of analytes；（5） exploring how the higher magnetic field influences extraction efficiency by designing new magnetic-field-regulating devices with small thermal interference；（6） combining the technology with advanced portable analytical instruments to realize real-time target analysis in the field；（7） exploiting immuno-affinitive extraction tubes that can be used to highly efficiently and selectively extract biological macromolecular drugs.

Key words: magnetism-enhanced in-tube solid-phase microextraction （ME-IT-SPME）, sample preparation, environmental analysis, food analysis, biomedicine analysis, review

CLC Number:

O658

LUO Yana, CHEN Jia, HU Yuyu, GAO Shijie, WANG Yanli, LIU Yanming, FENG Juanjuan, SUN Min. Research progress in material preparation and application of magnetism-enhanced in-tube solid-phase microextraction[J]. Chinese Journal of Chromatography, 2025, 43(6): 606-619.

Figures/Tables 10

Fig. 1 （a） Preparation sketch of VPED-MCC/MNPs［13］ and （b） polymerization schematic of MCEN［14］VPED-MCC/MNPs： poly（4-vinylpyridine （VP）-co-ethylene dimethacrylate （ED））-based monolithic capillary column （MCC） containing magnetic nanoparticles （MNPs）； MCEN： poly（4-vinylphenylboronic acid （VA）-co-ED）-based monolithic capillary microextraction column embedded with Fe3O4 magnetic nanoparticles； AIBN： 2，2′-azobis（2-methylpropionitrile）.

Fig. 2 Schematic diagram of raw material and product structure of PIL-MCC/MNPs［15］PIL-MCC/MNPs： poly（1-allyl-3-methylimidazolium bis（trifluoromethylsulfonyl）imide （AM）-co-ED）-based monolithic capillary column doped with magnetic nanoparticles.

Fig. 3 Polymerization schematic of MBCC［18］MBCC： poly（4-vinylbenzoic acid （VBA）-co-ED） monolith-based capillary column.

Fig. 4 In situ synthesis sketches of （a） TPM@MEC［20］ and （b） MBMC［22］TPM@MEC： task specific porous poly（AMI-co-DVB-co-VA） embedded magnetic nanoparticles as microextraction column； MBMC： poly（VI-co-ED-co-AMI） monolith mingled with Fe3O4 nanoparticles； AMI： 1-allyl-3-methylimidazolium bis（trifluoromethylsulfonyl）imide； DVB： divinylbenzene； VA： 9-vinylanthracene； VI： vinylimidazole.

Fig. 5 Chromatograms of sulfonylurea herbicides （a） without enrichment， and after enrichment with （b） IT-SPME and （c） ME-IT-SPME［17］ME-IT-SPME： magnetism-enhanced in-tube solid-phase microextraction； THM： thifensulfuron methyl； MEM： metsulfuron methyl； CHS： chlorsulfuron； PRS： prosulfuron； TRM： triflulsulfuron methyl.

Fig. 6 Chromatograms of six triazine herbicides （a） before enrichment， and after enrichment with （b） IT-SPME and （c） ME-IT-SPME［26］SIM： simazine； ATO： atraton； ATZ： atrazine； TEM： terbumeton； PRO： prometryne； TET： trietazine.

Fig. 7 Chromatograms of Cr（Ⅵ）/APD and Cr（Ⅲ）/APD （a） before enrichment， and after enrichment with （b） IT-SPME and （c） ME-IT-SPME［18］APD： ammonium pyrrolidine dithiocarbamate.

Fig. 8 Schematic of the developed ME-IT-SPME system［35］

Fig. 9 Chromatograms of organotin compounds （a） before enrichment， and after enrichment with （b） IT-SPME and （c） ME-IT-SPME［20］DPhT： diphenyl tin； TBT： tributyl tin； TPhT： triphenyltin.

Fig. 10 Chromatograms of tetraethyllead （TEL）（a） before enrichment， and after enrichment with （b） IT-SPME and （c） ME-IT-SPME［43］

References

1	Zheng J， Kuang Y X， Zhou S X， et al. Anal Chem， 2023， 95（1）： 218
2	Li X， Wen X X， Luo Z W， et al. Clin Chim Acta， 2023， 540： 117236
3	Sun M， Feng J J， Han S， et al. Microchim Aata， 2021， 188（3）： 96
4	Ali J， Tuzen M， Jatoi W B， et al. Food Chem， 2024， 437： 137908
5	Costa Queiroz M E， Donizeti de Souza I， Marchioni C. TrAC-Trends Anal Chem， 2019， 111： 261
6	Sun M， Bu Y N， Xin X B， et al. Microchem J， 2022， 181： 107699
7	Ma R， Yu S S， Li Y F， et al. Front Environ Sci， 2024， 12： 1350170
8	Sun M， Han S， Maloko Loussala H， et al. Microchem J， 2021， 166： 106263
9	Winkleman A， Gudiksen K L， Ryan D， et al. Appl Phys Lett， 2004， 85（12）： 2411
10	Watarai H， Namba M. J Chromatogr A， 2002， 961（1）： 3
11	Moliner-Martínez Y， Prima Garcia H， Ribera A， et al. Anal Chem， 2012， 84（16）： 7233
12	Manbohi A， Ahmadi S H. Anal Chim Acta， 2015， 885： 114
13	Mei M， Huang X J， Luo Q， et al. Anal Chem， 2016， 88（3）： 1900
14	Mei M， Pang J L， Huang X J， et al. Anal Chim Acta， 2019， 1090： 82
15	Mei M， Huang X J. J Chromatogr A， 2017， 1525： 1
16	Chen H X， Song X C， Huang X J. J Sep Sci， 2021， 44（18）： 3418
17	Pang J L， Song X C， Huang X J， et al. J Chromatogr A， 2020， 1613： 460672
18	Pang J L， Chen H X， Huang X J. Microchem J， 2021， 164： 105956
19	Song X C， Wu J Y， Pang J L， et al. J Hazard Mater， 2021， 411： 125141
20	Song X C， Luo Q， Huang X J. Anal Chim Acta， 2022， 1223： 340175
21	Song X C， Luo S Y， Liu J， et al. The Analyst， 2022， 147（7）： 1499
22	Song X C， Peng M M， Luo Q， et al. Talanta， 2023， 270： 125528
23	Moliner-Martinez Y， Vitta Y， Prima Garcia H， et al. Anal Bioanal Chem， 2014， 406（8）： 2211
24	Ma J P， Xia Y， Lu W H， et al. J Chromatogr A， 2016， 1466： 12
25	Yang J H， Zhou X M， Zhang Y P， et al. Adsorpt Sci Technol， 2017， 35（3）： 372
26	Mei M， Huang X J， Yang X D， et al. Anal Chim Acta， 2016， 937： 69
27	Zhao R S， Yuan J P， Jiang T， et al. Talanta， 2008， 76（4）： 956
28	Sorouraddin S M， Farajzadeh M A， Okhravi T. Talanta， 2017， 175： 359
29	Werner J. Talanta， 2018， 182： 69
30	Rofouei M K， Jamshidi S， Seidi S， et al. Microchim Acta， 2017， 184（9）： 3425
31	Ghiasi A， Malekpour A. Microchem J， 2020， 154： 104530
32	Hsu K C， Sun C C， Ling Y C， et al. J Anal At Spectrom， 2013， 28（8）： 1320
33	Gao Z B， Ma X G. Anal Chim Acta， 2011， 702（1）： 50
34	He Y F， He M， Nan K， et al. J Chromatogr A， 2019， 1595： 19
35	Song X C， Pang J L， Wu Y F， et al. Microchem J， 2020， 159： 105370
36	Kaur V， Malik A K. Talanta， 2007， 73（3）： 425
37	Farajzadeh M A， Yadeghari A. J Ind Eng Chem， 2018， 59： 377
38	Rohanifar A， Rodriguez L B， Devasurendra A M， et al. Talanta， 2018， 188： 570
39	Hu H， Tu W， Chen Y， et al. J Cancer， 2020， 11（8）： 2022
40	González Toledo E， Benzi M， Compano R， et al. Anal Chim Acta， 2001， 443（2）： 183
41	Quintas P Y， Alvarez M B， Arias A H， et al. Environ Sci Pollut Res， 2019， 26（8）： 7601
42	González Toledo E， Compano R， Granados M， et al. J Chromatogr A， 2000， 878（1）： 69
43	Song X C， Meng X， Chen M S， et al. J Chromatogr A， 2023， 1700： 464040
44	Song W L， Guo M， Zhang Y D， et al. J Chromatogr A， 2015， 1384： 28
45	Vidal L， Chisvert A， Canals A， et al. Talanta， 2010， 81（1）： 549
46	Clavijo S， Avivar J， Suárez R， et al. J Chromatogr A， 2016， 1443： 26
47	Uluozlü D. At Spectrosc， 2019， 40（4）： 133
48	Kalantari H， Manoochehri M. Microchim Acta， 2018， 185（3）： 196
49	Peng L Q， Yi L， Yang Q C， et al. Sci Rep， 2017， 7（1）： 7496
50	Shi S， Fan D， Xiang H， et al. Food Chem， 2017， 237： 198
51	Xu J， Chen B， He M， et al. J Chromatogr A， 2013， 1278： 8
52	Tashakkori P， Tagac A A， Merdivan M. J Chromatogr A， 2021， 1635： 461741
53	Mei M， Pang J L， Huang X J. Anal Methods， 2018， 10（17）： 1977
54	Chen W， Huang H F， Chen C E， et al. Chemosphere， 2016， 163： 99
55	Uslu M， Ulutürk H， Yartasi A， et al. Toxicol Environ Chem， 2013， 95（10）： 1638
56	Dadfarnia S， Haji Shabani A M， Dehghanpoor F. J Sep Sci， 2016， 39（8）： 1509
57	Xu S， Jiang C， Lin Y X， et al. Microchim Acta， 2012， 179（3）： 257
58	Marazuela M D， Moreno Bondi M C. J Chromatogr A， 2004， 1034（1）： 25
59	Ramos Payán M， Bello López M A， Fernández Torres R， et al. J Pharm Biomed Anal， 2011， 55（2）： 332

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