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Removal of multiple lipids from human plasma using a hydroxyl-functionalized covalent organic framework aerogel as a new sorbent

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Abstract

A hydroxyl-functionalized covalent organic framework aerogel COFTHB-TAPB-aerogel was designed and prepared as an adsorbent for the removal of multiple lipids from human plasma. The applications of 1,3,5-tris(4′-hydroxy-5′-formylphenyl)benzene (THB) and 1,3,5-tris(4-aminophenyl)benzene (TAPB) as monomers, DMSO/mesitylene (v/v, 4/1) as reaction solvent, and n-propylamine as reaction regulator endow COFTHB-TAPB-aerogel with good adsorption performance for multiple lipids. The morphology, phase purity, specific surface area, pore size, surface charge, and stability of COFTHB-TAPB-aerogel were characterized. Adsorption thermodynamics and adsorption kinetics studies showed that COFTHB-TAPB-aerogel had high equilibrium adsorption capacities (> 15913 mg g−1) and fast adsorption equilibrium (≤ 10 s) for the four model lipids tested. COFTHB-TAPB-aerogel had good reusability with the removal of the model lipids being still more than 91% after 10 use cycles. The sample pretreatment conditions and adsorbent amounts used in lipids removal experiments were optimized. Under the optimized conditions, the method of ultra-high performance liquid chromatography–high-resolution mass spectrometry (UHPLC–HRMS) using COFTHB-TAPB-aerogel as solid-phase extraction sorbent was validated with negligible matrix effects (0.4–3.0%) and good accuracy (86.7–110%) and was applied to determine  20 amino acids in human plasma samples from healthy individuals and gastric adenocarcinoma (GA) patients. The established method has been proved to have good application potential for the removal of multiple lipids in human plasma to reduce the matrix effects and improve the accuracy of clinical LC–MS analysis.

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References

  1. Hopfgartner G, Bourgogne E (2003) Quantitative high-throughput analysis of drugs in biological matrices by mass spectrometry. Mass Spectrom Rev 22:195–214. https://doi.org/10.1002/mas.10050

    Article  CAS  PubMed  Google Scholar 

  2. Ismaiel OA, Zhang T, Jenkins RG, Karnes HT (2010) Investigation of endogenous blood plasma phospholipids, cholesterol and glycerides that contribute to matrix effects in bioanalysis by liquid chromatography/mass spectrometry. J Chromatogr B 878:3303–3316. https://doi.org/10.1016/j.jchromb.2010.10.012

    Article  CAS  Google Scholar 

  3. Dams R, Huestis MA, Lambert WE, Murphy CM (2003) Matrix effect in bio-analysis of illicit drugs with LC–MS/MS: influence of ionization type, sample preparation, and biofluid. J Am Soc Mass Spectrom 14:1290–1294. https://doi.org/10.1016/S1044-0305(03)00574-9

    Article  CAS  PubMed  Google Scholar 

  4. Guo X, Lankmayr E (2011) Phospholipid-based matrix effects in LC–MS bioanalysis. Bioanalysis 3:349–352. https://doi.org/10.4155/BIO.10.213

    Article  CAS  PubMed  Google Scholar 

  5. Maldonadoa EN, Romero JR, Ochoab B, Aveldaño MI (2001) Lipid and fatty acid composition of canine lipoproteins. Comp Biochem Physiol Part B 128:719–729. https://doi.org/10.1016/S1096-4959(00)00366-3

    Article  Google Scholar 

  6. Teo CC, Chong WPK, Tan E, Basri NB, Low ZJ, Ho YS (2015) Advances in sample preparation and analytical techniques for lipidomics study of clinical samples. TrAC Trends Anal Chem 66:1–18. https://doi.org/10.1016/j.trac.2014.10.010

    Article  CAS  Google Scholar 

  7. Tulipani S, Mora-Cubillos X, Jauregui O, Llorach R, Garcia-Fuentes E, Tinahones FJ, Andres-Lacueva C (2015) New and vintage solutions to enhance the plasma metabolome coverage by LC-ESI-MS untargeted metabolomics: the not-so-simple process of method performance evaluation. Anal Chem 87:2639–2647. https://doi.org/10.1021/ac503031d

    Article  CAS  PubMed  Google Scholar 

  8. Flieger J, Tatarczak-Michalewska M, Kowalska A, Madejska A, Sniegocki T, Sroka-Bartnicka A, Szymanska-Chargot M (2017) Effective phospholipid removal from plasma samples by solid phase extraction with the use of copper(II) modified silica gel cartridges. J Chromatogr B 1070:1–6. https://doi.org/10.1016/j.jchromb.2017.10.021

    Article  CAS  Google Scholar 

  9. Li H, Shi X, Qiao L, Lu X, Xu G (2013) Synthesis of a new type of echinus-like Fe3O4@TiO2 core-shell-structured microspheres and their applications in selectively enriching phosphopeptides and removing phospholipids. J Chromatogr A 1275:9–16. https://doi.org/10.1016/j.chroma.2012.12.023

    Article  CAS  PubMed  Google Scholar 

  10. Li L, Chen Y, Yang L, Wang Z, Liu H (2020) Recent advances in applications of metal-organic frameworks for sample preparation in pharmaceutical analysis. Coord Chem Rev 411:1–15. https://doi.org/10.1016/j.ccr.2020.213235

    Article  CAS  Google Scholar 

  11. Gomes R, Bhanja P, Bhaumik A (2015) A triazine-based covalent organic polymer for efficient CO2 adsorption. Chem Commun (Camb) 51:10050–10053. https://doi.org/10.1039/c4an00094c

    Article  CAS  PubMed  Google Scholar 

  12. Li J, Xu X, Wang X, Li C, Feng X, Zhang Y, Zhang F (2022) Construction of a magnetic covalent organic framework for magnetic solid-phase extraction of AFM1 and AFM2 in milk prior to quantification by LC-MS/MS. Microchim Acta 189:1–10. https://doi.org/10.1007/s00604-021-05090-8

    Article  CAS  Google Scholar 

  13. Deng ZH, Wang X, Wang XL, Gao CL, Dong L, Wang ML, Zhao RS (2019) A core-shell structured magnetic covalent organic framework (type Fe3O4@COF) as a sorbent for solid-phase extraction of endocrine-disrupting phenols prior to their quantitation by HPLC. Mikrochim Acta 186:1–10. https://doi.org/10.1007/s00604-018-3198-3

    Article  CAS  Google Scholar 

  14. Milcovich G, Lettieri S, Antunes FE, Medronho B, Fonseca AC, Coelho JFJ, Marizza P, Perrone F, Farra R, Dapas B, Grassi G, Grassi M, Giordani S (2017) Recent advances in smart biotechnology: hydrogels and nanocarriers for tailored bioactive molecules depot. Adv Colloid Interface Sci 249:163–180. https://doi.org/10.1016/j.cis.2017.05.009

    Article  CAS  PubMed  Google Scholar 

  15. Zhang J, Liu L, Liu H, Lin M, Li S, Ouyang G, Chen L, Su CY (2015) Highly porous aerogels based on imine chemistry: syntheses and sorption properties. J Mater Chem A 3:10990–10998. https://doi.org/10.1039/C5TA00557D

    Article  CAS  Google Scholar 

  16. Martin-Illan JA, Rodriguez-San-Miguel D, Castillo O, Beobide G, Perez-Carvajal J, Imaz I, Maspoch D, Zamora F (2021) Macroscopic ultralight aerogel monoliths of imine-based covalent organic frameworks. Angew Chem Int Ed 60:13969–13977. https://doi.org/10.1002/anie.202100881

    Article  CAS  Google Scholar 

  17. Du ML, Yang C, Qian HL, Yan XP (2022) Hydroxyl-functionalized three-dimensional covalent organic framework for selective and rapid extraction of organophosphorus pesticides. J Chromatogr A 1673:1–8. https://doi.org/10.1016/j.chroma.2022.463071

    Article  CAS  Google Scholar 

  18. Zhao Z, Liang B, Wang M, Yang Q, Su M, Liang S (2022) Microporous carbon derived from hydroxyl functionalized organic network for efficient adsorption of flumequine: adsorption mechanism and application potentials. Chem Eng J 427:1–13. https://doi.org/10.1016/j.cej.2021.130943

    Article  CAS  Google Scholar 

  19. Xu M, An Y, Wang Q, Wang J, Hao L, Wang C, Wang Z, Zhou J, Wu Q (2021) Construction of hydroxyl functionalized magnetic porous organic framework for the effective detection of organic micropollutants in water, drink and cucumber samples. J Hazard Mater 412:1–13. https://doi.org/10.1016/j.jhazmat.2021.125307

    Article  CAS  Google Scholar 

  20. Wang L, Tao Y, Wang J, Tian M, Liu S, Quan T, Yang L, Wang D, Li X, Gao D (2022) A novel hydroxyl-riched covalent organic framework as an advanced adsorbent for the adsorption of anionic azo dyes. Anal Chim Acta 1227:1–13. https://doi.org/10.1016/j.aca.2022.340329

    Article  CAS  Google Scholar 

  21. Yin F, Ling Y, Martin J, Narayanaswamy R, McIntosh L, Li F, Liu G (2021) Quantitation of uridine and L-dihydroorotic acid in human plasma by LC-MS/MS using a surrogate matrix approach. J Pharm Biomed Anal 192:1–11. https://doi.org/10.1016/j.jpba.2020.113669

    Article  CAS  Google Scholar 

  22. Zhu D, Zhu Y, Yan Q, Barnes M, Liu F, Yu P, Tseng CP, Tjahjono N, Huang PC, Rahman MM, Egap E, Ajayan PM, Verduzco R (2021) Pure crystalline covalent organic framework aerogels. Chem Mater 33:4216–4224. https://doi.org/10.1021/acs.chemmater.1c01122

    Article  CAS  Google Scholar 

  23. Zhao W, Wang TP, Wu JL, Pan RP, Liu XY, Liu XK (2019) Monolithic covalent organic framework aerogels through framework crystallization induced self-assembly: heading towards framework materials synthesis over all length scales. Chin J Polym Sci 37:1045–1052. https://doi.org/10.1007/s10118-019-2313-1

    Article  CAS  Google Scholar 

  24. Vitaku E, Dichtel WR (2017) Synthesis of 2D imine-linked covalent organic frameworks through formal transimination reactions. J Am Chem Soc 139:12911–12914. https://doi.org/10.1021/jacs.7b06913

    Article  CAS  PubMed  Google Scholar 

  25. Li H, Feng X, Shao P, Chen J, Li C, Jayakumar S, Yang Q (2019) Synthesis of covalent organic frameworks via in situ salen skeleton formation for catalytic applications. J Mater Chem A 7:5482–5492. https://doi.org/10.1039/c8ta11058a

    Article  CAS  Google Scholar 

  26. Mao C, Hu Y, Yang C, Qin C, Dong G, Zhou Y, Zhang Y (2021) Well-designed spherical covalent organic frameworks with an electron-deficient and conjugate system for efficient photocatalytic hydrogen evolution. ACS Appl Energy Mater 4:14111–14120. https://doi.org/10.1021/acsaem.1c02874

    Article  CAS  Google Scholar 

  27. Ma W, Zheng Q, He Y, Li G, Guo W, Lin Z, Zhang L (2019) Size-controllable synthesis of uniform spherical covalent organic frameworks at room temperature for highly efficient and selective enrichment of hydrophobic peptides. J Am Chem Soc 141:18271–18277. https://doi.org/10.1021/jacs.9b09189

    Article  CAS  PubMed  Google Scholar 

  28. Lin YF, Chen JH, Hsu SH, Hsiao HC, Chung TW, Tung KL (2012) The synthesis of lewis acid ZrO2 nanoparticles and their applications in phospholipid adsorption from jatropha oil used for biofuel. J Colloid Interface Sci 368:660–662. https://doi.org/10.1016/j.jcis.2011.11.055

    Article  CAS  PubMed  Google Scholar 

  29. Zhang Y, Zhang G, Liu W, Li M, Jiang S, Hao L, Wang Z, Wu Q, Wang C (2021) Fabrication of carbonyl-functional hypercrosslinked polymers as solid-phase extraction sorbent for enrichment of chlorophenols from water, honey and beverage samples. Mikrochim Acta 189:1–10. https://doi.org/10.1007/s00604-021-05123-2

    Article  CAS  Google Scholar 

  30. Wang M, Gao M, Zhang K, Wang L, Wang W, Fu Q, Xia Z, Gao D (2019) Magnetic covalent organic frameworks with core-shell structure as sorbents for solid phase extraction of fluoroquinolones, and their quantitation by HPLC. Mikrochim Acta 186:1–13. https://doi.org/10.1007/s00604-019-3757-2

    Article  CAS  Google Scholar 

  31. Zhang L, Zheng W, Li X, Wang S, Xiao M, Xiao R, Zhang D, Ke N, Cai H, Cheng J, Chen X, Gong M (2021) A merged method for targeted analysis of amino acids and derivatives using parallel reaction monitoring combined with untargeted profiling by HILIC-Q-Orbitrap HRMS. J Pharm Biomed Anal 203:1–11. https://doi.org/10.1016/j.jpba.2021.114208

    Article  CAS  Google Scholar 

  32. Prinsen H, Schiebergen-Bronkhorst BGM, Roeleveld MW, Jans JJM, de Sain-van der Velden MGM, Visser G, van Hasselt PM, Verhoeven-Duif NM (2016) Rapid quantification of underivatized amino acids in plasma by hydrophilic interaction liquid chromatography (HILIC) coupled with tandem mass-spectrometry. J Inherited Metab Dis 39:651–660. https://doi.org/10.1007/s10545-016-9935-z

    Article  CAS  PubMed  Google Scholar 

  33. Hoyos OD, Cuartas OY, Penuela MG (2017) Development and validation of a highly sensitive quantitative/confirmatory method for the determination of ivermectin residues in bovine tissues by UHPLC-MS/MS. Food Chem 221:891–897. https://doi.org/10.1016/j.foodchem.2016.11.077

    Article  CAS  Google Scholar 

  34. Hu YL, Pang W, Huang Y, Zhang Y, Zhang CJ (2018) The gastric microbiome is perturbed in advanced gastric adenocarcinoma identified through shotgun metagenomics. Front Cell Infect Microbiol 8:1–11. https://doi.org/10.3389/fcimb.2018.00433

    Article  CAS  Google Scholar 

  35. Liu J, Lin S, Li Z, Zhou L, Yan X, Xue Y, Meng L, Lu J, Suo B, Jiang W (2018) Free amino acid profiling of gastric juice as a method for discovering potential biomarkers of early gastric cancer. Int J Clin Exp Pathol 11:2323–2336

    PubMed  PubMed Central  Google Scholar 

  36. Song H, Wang L, Liu HL, Wu XB, Wang HS, Liu ZH, Li Y, Diao DC, Chen HL, Peng JS (2011) Tissue metabolomic fingerprinting reveals metabolic disorders associated with human gastric cancer morbidity. Oncol Rep 26:431–438. https://doi.org/10.3892/or.2011.1302

    Article  CAS  PubMed  Google Scholar 

  37. Choi MS, Rehman SU, Kim IS, Park HJ, Song MY, Yoo HH (2017) Development of a mixed-mode chromatography with tandem mass spectrometry method for the quantitative analysis of 23 underivatized amino acids in human serum. J Pharm Biomed Anal 145:52–58. https://doi.org/10.1016/j.jpba.2017.06.040

    Article  CAS  PubMed  Google Scholar 

  38. Ozturk Er E, Ozbek B, Bakirdere S (2021) Determination of seventeen free amino acids in human urine and plasma samples using quadruple isotope dilution mass spectrometry combined with hydrophilic interaction liquid chromatography-tandem mass spectrometry. J Chromatogr A 1641:1–8. https://doi.org/10.1016/j.chroma.2021.461970

    Article  CAS  Google Scholar 

  39. Li Z, Wu J, Jia L (2019) Analysis of amino acids in blood by combining zeolitic imidazolate framework-8-based solid phase extraction and capillary electrophoresis. J Pharm Biomed Anal 168:30–37. https://doi.org/10.1016/j.jpba.2019.02.015

    Article  CAS  PubMed  Google Scholar 

  40. Tang XX, Gu Y, Cai S, Xu ML, Wang C (2012) Analysis of amino acids in rat plasma by solid phase extraction-high performance liquid chromatography-electrospray tandem mass spectrometry and the application to radiation injury rat model. Chin J Chromatogr 30:696–704. https://doi.org/10.3724/SP.J.1123.2012.01037

    Article  CAS  Google Scholar 

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Funding

This work was financially supported by the National Key Research and Development Program of China (No. 2018YFC1602403) and the Youth Innovation Promotion Association, CAS (2019316).

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Authors and Affiliations

  1. Chengdu Institute of Biology, Chinese Academy of Sciences, Chengdu, 610041, China

    Peiyu Shi, Bing Xia & Yan Zhou

  2. University of Chinese Academy of Sciences, Beijing, 100049, China

    Peiyu Shi

  3. Chengdu Institute of Food Inspection, Chengdu, 611135, China

    Peiyu Shi

  4. Clinical Pharmacology Lab, Clinical Trial Center, West China Hospital, Sichuan University, Chengdu, 610041, China

    Yongping Qin

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  1. Peiyu Shi
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Shi, P., Xia, B., Qin, Y. et al. Removal of multiple lipids from human plasma using a hydroxyl-functionalized covalent organic framework aerogel as a new sorbent. Microchim Acta 190, 222 (2023). https://doi.org/10.1007/s00604-023-05770-7

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