Skip to main content
SpringerLink
Log in

Monolithic Column Prepared with UiO-66-2COOH MOF as Monomer for Enrichment and Purification of Ursolic Acid in Plants by Online Solid-Phase Extraction

  • Original
  • Published:
Chromatographia Aims and scope Submit manuscript

Abstract

A method for preparing a metal–organic framework (MOF)–polymeric monolith was established by in situ radical polymerization with derivatized UiO-66-2COOH and N-isopropylacrylamide (NIPAAm) as co-monomers. It was worth noting that the obtained monolith possessed characteristics of relatively uniform porous structure and a high surface area (84.16 m2 g−1). The adsorption capacity of the monolith increased from 22.87 to 44.92 mg−1 due to the addition of MOF. The monolith was used as adsorbent and coupled with HPLC for the online purification and extraction of ursolic acid (UA) in medicinal plant. The limit of detection (LOD, S/N = 3) and the limit of quantification (LOQ, S/N = 10) were 0.17 μg mL−1 and 0.57 μg mL−1, respectively; the relative standard deviation (RSD) of intra-day and inter-day assays for five plant samples were 1.00–3.67% and 2.43–5.76%, respectively; a good accuracy was demonstrated by the recovery of 92.2–103.28%. The results indicated that the MOF–polymer monolith was feasible for the online enrichment and purification of UA in plant.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Seo DY, Lee SR, Heo JW, No MH, Rhee BD, Ko KS, Kwak HB, Han J (2018) Ursolic acid in health and disease. Korean J Physiol Pharmacol 22:235–248

    Article  CAS  Google Scholar 

  2. Pironi AM, de Araújo PR, Fernandes MA, Nunes Salgado HR, Chorilli M (2018) Characteristics, biological properties and analytical methods of ursolic acid: a review. Crit Rev Anal Chem 48:86–93

    Article  CAS  Google Scholar 

  3. Ikeda Y, Murakami A, Ohigashi H (2008) Ursolic acid: an anti- and pro-inflammatory triterpenoid. Mol Nutr Food Res 52:26–42

    Article  CAS  Google Scholar 

  4. Li S, Liao X, Meng F (2014) Therapeutic role of ursolic acid on ameliorating hepatic steatosis and improving metabolic disorders in high-fat diet-induced non-alcoholic fatty liver disease rats. PLoS ONE 9:e92364

    Article  Google Scholar 

  5. Lin J, Chen Y, Wei L, Hong Z, Sferra TJ, Peng J (2013) Ursolic acid inhibits colorectal cancer angiogenesis through suppression of multiple signaling pathways. Int J Oncol 43:1666–1674

    Article  CAS  Google Scholar 

  6. Hsu HY, Yang JJ, Lin CC (1997) Effects of oleanolic acid and ursolic acid on inhibiting tumor growth and enhancing the recovery of hematopoietic system postirradiation in mice. Cancer Lett 111:7–13

    Article  CAS  Google Scholar 

  7. Abe F, Yamauchi T, Nagao T, Kinjo J, Okabe H, Higo H, Akahane H (2002) Ursolic acid as a trypanocidal constituent in rosemary. Biol Pharm Bull 25:1485–1487

    Article  CAS  Google Scholar 

  8. Ladislav N, Mohammed EAH, Hoda H, Irena M, Daniel G (2003) Development of LC–MS method for determination of ursolic acid: application to the analysis of ursolic acid in Staphylea holocarpa Hemsl. J Pharm Biomed Anal 5:961–968

    Google Scholar 

  9. Xia EQ, Wang BW, Xu XR, Zhu L, Song Y, Li HB (2011) Microwave-assisted extractin of oleanolic acid and ursolic acid from Ligustrum lucidum Ait. J Mole Sci 12:5319–5329

    Article  CAS  Google Scholar 

  10. Xia EQ, Yu YY, Xu XR, Deng GF, Guo YJ, Li HB (2012) Ultrasound-assisted extraction of oleanolic acid and ursolic acid from Ligustrum lucidum Ait. Ultrason Sonochem 19:772–776

    Article  CAS  Google Scholar 

  11. Magdalena WK, Ireneusz S, Ryszard K, Renata N (2013) Effect of different extraction techniques on quantification of oleanolic and ursolic acid in Lamii albi flos. Ind Crops Prod 44:373–377

    Article  Google Scholar 

  12. Huang LY, Chen TW, Ye Z, Chen GN (2007) Use of liquid chromatography–atmospheric pressure chemical ionization–ion trap mass spectrometry for identification of oleanolic acid and ursolic acid in Anoectochilus roxburghii (wall.) Lindl. J Mass Spectrom 42:910–917

    Article  CAS  Google Scholar 

  13. Tarvainen M, Suomela JP, Kallio H, Yang B (2010) Triterpene acids in plantago major: identification, quantification and comparison of different extraction methods. Chromatographia 71:279–284

    Article  CAS  Google Scholar 

  14. Wang LY, Ni CF, Shen HL, Sheng ZH, Liang C, Wang R, Zhang YR (2020) Comparison of the detection windows of heroin metabolites in human urine using online SPE and LC–MS/MS: importance of morphine-3-glucuronide. J Anal Toxicol 44(1):22–28

    PubMed  Google Scholar 

  15. Zhang JM, Lin WS, Li XN, Yu N, Ling XM, Fu G, Li RT, Cui JR (2012) Determination of 4-methylpiperaine-1-carbodithioc acid 3-cyano-3, 3-diphenylpropyl ester hydrochloride in rats' plasma by online-SPE-HPLC-DAD: application to a pharmacokinetic study. J Sep Sci 35:721–725

    Article  CAS  Google Scholar 

  16. Liu HM, Liu CH, Yang XJ, Zeng SJ, Xiong YQ, Xu WJ (2008) Uniformly sized beta-cyclodextrin molecularly imprinted microspheres prepared by a novel surface imprinting technique for ursolic acid. Anal Chim Acta 628:87–94

    Article  CAS  Google Scholar 

  17. Janicsák G, Veres K, Kállai M, Máthé L (2003) Gas chromatographic method for routine determination of oleanolic and ursolic acids in medicinal plants. Chromatographia 58:295–299

    Google Scholar 

  18. Svec F, Lv Y (2015) Advances and recent trends in the field of monolithic columns for chromatography. Anal Chem 87:250–273

    Article  CAS  Google Scholar 

  19. Zhang Z, Yan X, Sun L, Zhu G, Dovichi NJ (2015) A detachable strong cation exchange monolith, integrated with capillary zone electrophoresis and coupled with pH gradient elution, produces improved sensitivity and numbers of peptide identifications during bottom-up analysis of complex proteomes. Anal Chem 87:4572–4577

    Article  CAS  Google Scholar 

  20. Lin H, Ou JJ, Liu ZS, Wang HW, Dong J, Zou F (2015) Thiol-epoxy click polymerization for preparation of polymeric monoliths with well-defined 3D framework for capillary liquid chromatography. Anal Chem 87:3476–3483

    Article  CAS  Google Scholar 

  21. Zhu T, Li SN, Row KH (2011) Molecularly imprinted monolithic material for the extraction of three organic acids from Salicornia herbacea L. J Appl Polym Sci 121:1691–1696

    Article  CAS  Google Scholar 

  22. Zhu T, Park HE, Row KH (2013) Ultrasonic-assisted extraction of tanshinones from Korean red ginseng by using amino-modified monolithic cartridge. Asian J Chem 25:7765–7768

    Article  CAS  Google Scholar 

  23. Sun YK, Sun GY, Jia M, Yang J, Liu ZS, Huang YP, Aisa HA (2019) Cost-effective imprinting to minimize consumption of template in room-temperature ionic liquid for fast purification of chlorogenic acid from the extract of E. ulmoides leaves. Anal Bioanal Chem 411:1261–1271

    Article  CAS  Google Scholar 

  24. Nian QX, Ai LF, Li DM, Chen XL, Zhang L, Wang MM, Wang XS (2018) Rapid monitoring of plant growth regulators in bean sprouts via automated on-line polymeric monolith solid-phase extraction coupled with liquid chromatography tandem mass spectrometry. Anal Bioanal Chem 410:7239–7247

    Article  CAS  Google Scholar 

  25. Ma W, Li XJ, Bai Y, Liu HW (2018) Applications of metal–organic frameworks as advanced sorbents in biomacromolecules sample preparation. Trends Anal Chem 109:154–162

    Article  CAS  Google Scholar 

  26. Mansour O, Kawas G, Rasheed MA, Sakur AA (2018) Applications of metal–organic frameworks (MOFs) to separation analytical techniques research. J Pharm Technol 11:3514–3522

    Google Scholar 

  27. Duan JG, Yan R, Qin LL, Wang Y, Wen LL, Cheng SX, Xu H, Feng PY (2018) Highly selective gaseous and liquid-phase separation over a novel cobalt(II) metal−organic framework. ACS Appl Mat Interfraces 10:23009–23017

    Article  CAS  Google Scholar 

  28. Wang X, Ye NS (2017) Recent advances in metal–organic frameworks and covalent organic frameworks for sample preparation and chromatographic analysis. Electrophoresis 38:3059–3078

    Article  CAS  Google Scholar 

  29. Maya F, Cabello CP, Estela JM, Cerdà V, Palomino GT (2015) Automatic in-syringe dispersive microsolid phase extraction using magnetic metal−organic frameworks. Anal Chem 87:7545–7549

    Article  CAS  Google Scholar 

  30. Yang SC, Ye FG, Lv QH, Zhang C, Shen SF, Zhao SL (2014) Incorporation of metal–organic framework HKUST-1 into porous Polymer monolithic capillary columns to enhance the chromatographic separation of small molecules. J Chromatogr A 1360:143–149

    Article  CAS  Google Scholar 

  31. Huang HY, Lin CL, Wu CY, Cheng YJ, Lin CH (2013) Metal organic framework–organic polymer monolith stationary phases for capillary electrochromatography and nano-liquid chromatography. Anal Chim Acta 779:96–103

    Article  CAS  Google Scholar 

  32. Pang XY, Liu HY, Yu H, Zhang MM, Bai LG, Yan HY (2019) A metal organic framework polymer monolithic column as a novel adsorbent for on-line solid phase extraction and determination of ursolic acid in Chinese herbal medicine. J Chromatogr B 1125:121715

    Article  CAS  Google Scholar 

  33. Zhao XD, Liu DH, Huang HL, Zhong CL (2016) Highly selective and sensitive metal–organic framework fluorescent probe for Cu2+ through rational design of binding sites. Micropor Mesopor Mat 224:149–154

    Article  CAS  Google Scholar 

  34. Zhang GQ, Qi YP, Lou ZY, Liu CH, Wu XF, Chai YF (2007) Determination of oleanolic acid and ursolic acid in cornel by cyclodextrin-modified micellar electrokinetic chromatography. Biomed Chromatogr 7:529–532

    Google Scholar 

  35. Gao RB, Wang LT, Yang Y, Ni JM, Zhao L, Dong SQ, Guo M (2015) Simultaneous determination of oleanolic acid, ursolic acid, quercetin and apigenin in Swertia mussotii Franch by capillary zone electrophoresis with running buffer modifier. Biomed Chromatogr 29:402–409

    Article  Google Scholar 

  36. Caligiani A, Malavasi G, Palla G, Marseglia A, Tognolini M, Bruni R (2013) A simple GC–MS method for the screening of betulinic, corosolic, maslinic, oleanolic and ursolic acid contents in commercial botanicals used as food supplement ingredients. Food Chem 136:735–741

    Article  CAS  Google Scholar 

  37. Zheng ZJ, Zhao XE, Zhu SY, Dang J, Qiao XG, Qiu ZC, Tao YD (2018) Simultaneous determination of oleanolic acid and ursolic acid by in vivo microdialysis via UHPLC–MS/MS using magnetic dispersive solid phase extraction coupling with microwave-assisted derivatization and its application to a pharmacokinetic study of arctiumlappa l. root extract in rats. J Agric Food Chem 66:3975–3982

    Article  CAS  Google Scholar 

  38. Magdalena WK (2007) Separation and determination of closely related triterpenic acids by high performance thin-layer chromatography after iodine derivatization. J Pharm Biomed Anal 45:337–340

    Article  Google Scholar 

  39. Li GL, Zhang XL, You JM, Song CH, Sun ZW, Xia L, Suo YR (2011) Highly sensitive and selective pre-column derivatization high-performance liquid chromatography approach for rapid determination of triterpenes oleanolic and ursolic acids and application to Swertia species: optimization of triterpenic acids extraction and pre-column derivatization using response surface methodology. Anal Chim Acta 688:208–218

    Article  CAS  Google Scholar 

  40. Shen DD, Pan MH, Wu QL, Park CH, Juliani HR, Ho CT, Simon JE (2010) LC–MS method for the simultaneous quantitation of the anti-inflammatory constituents in Oregano (Origanum Species). J Agric Food Chem 58:7119–7125

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The work was supported by the National Natural Science Foundation of China (no. 21974034, 21575033, 21505030) and the Natural Science Foundation of Hebei Province (no. B2018201270).

Author information

Authors and Affiliations

  1. Key Laboratory of Public Health Safety of Hebei Province, College of Pharmacy, Hebei University, Baoding, 071002, China

    Xiaoya Pang, Haiyan Liu, Huan Yu, Miaomiao Zhang, Ligai Bai & Hongyuan Yan

  2. Key Laboratory of Medicinal Chemistry and Molecular Diagnosis of Ministry of Education, Institute of Life Science and Green Development, Hebei University, Baoding, 071002, China

    Xiaoya Pang, Haiyan Liu, Huan Yu, Miaomiao Zhang, Ligai Bai & Hongyuan Yan

Authors
  1. Xiaoya Pang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Haiyan Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Huan Yu
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Miaomiao Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Ligai Bai
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Hongyuan Yan
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Haiyan Liu or Hongyuan Yan.

Ethics declarations

Conflict of Interest

The authors declare that they have no conflict of interest.

Informed Consent

This article does not contain any studies with human participants or animals performed by any of the authors.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary file1 Fig. S1 Reaction equation of derivatized UiO-66-2COOH (TIF 1378 kb)

Supplementary file2 Fig. S2 PXRD pattern of UiO-66-2COOH (TIF 331 kb)

Supplementary file3 Fig. S3 FT-IR spectra of (a) UiO-66-2COOH and (b) derivatized UiO-66-2COOH (TIF 668 kb)

10337_2020_3931_MOESM4_ESM.tif

Supplementary file4 Fig. S4 Reaction equation and SEM images of MOF–polymer monolith (G) and poly (NIPAAm-co-EDMA) monolith (I) (TIF 4570 kb)

10337_2020_3931_MOESM5_ESM.tif

Supplementary file5 Fig. S5 The effect of methanol concentration on the retention factor of six aromatic compounds. Mobile phase: methanol/water (different ratio); Detection wavelength: 254 nm; Flow rate: 1.0 mL/min (TIF 535 kb)

10337_2020_3931_MOESM6_ESM.tif

Supplementary file6 Fig. S6 Separation of (a) neutral and (b) mixed samples with the MOF–polymer monolith. a: (1) benzene, (2) n-butylbenzene, (3) biphenyl, (4) anthracene; b: (1) catechol, (2) p-nitroaniline, (3) naphthalene; (4) diphenylamine, (5) anthracene (TIF 1044 kb)

10337_2020_3931_MOESM7_ESM.tif

Supplementary file7 Fig. S7 The back pressure of silica gel-C18 column (5 µm, 10 mm×4.6 mm i.d.) (a) and MOF–polymer monolith (50 mm×4.6 mm i.d.) (b) in different mobile phase (TIF 245 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Pang, X., Liu, H., Yu, H. et al. Monolithic Column Prepared with UiO-66-2COOH MOF as Monomer for Enrichment and Purification of Ursolic Acid in Plants by Online Solid-Phase Extraction. Chromatographia 83, 1121–1131 (2020). https://doi.org/10.1007/s10337-020-03931-x

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10337-020-03931-x

Keywords

Search

Navigation