Skip to main content
SpringerLink
Log in

A simple graphene-based pipette tip solid-phase extraction of malondialdehyde from human plasma and its determination by spectrofluorometry

  • Research Paper
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

Abstract

Determination of malondialdehyde (MDA) in human blood plasma is important because of its role as a biomarker of lipid peroxidation in biological and medical sciences. In this work, a miniaturized graphene-based pipette tip solid-phase extraction technique was developed for very efficient extraction of MDA as its dithiobarbituric acid (TBA) adduct from human plasma. Two milligrams of graphene as sorbent were placed into a pipette tip and MDA-TBA compound was extracted and preconcentrated by it, after 4 repeated aspirating/dispensing cycles, then the column was eluted with 80 μL of dimethyl sulfoxide by 4 repeated aspirating/dispensing cycles and elusion was measured spectrofluorimetrically. Various effective parameters such as type and volume of eluent solvent, temperature, sample volume, number of cycles of extraction and desorption, derivatization reaction time, and pH of the sample solution were investigated and optimized. Under optimum conditions, a linear calibration curve was obtained in the range of 0.5–90 μg L−1 (r 2 = 0.991) with a detection limit of 0.3 μg L−1. The relative standard deviations for 8 replicate measurements of 10 and 40 μg L−1 of MDA were found to be 4.51 and 3.78 % respectively. The developed protocol was successfully applied to the determination of MDA in a human blood plasma sample.

A simple graphene-based pipette tip solid-phase extraction of malondialdehyde from human plasma and its determination by spectrofluorometry

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
Fig. 7
Fig. 8

Similar content being viewed by others

References

  1. Yuksel S, Yigit AA. Malondialdehyde and nitric oxide levels and catalase, superoxide dismutase, and glutathione peroxidase levels in maternal blood during different trimesters of pregnancy and in the cord blood of newborns. Turk J Med Sci. 2015;45(2):454–9.

    Article  CAS  Google Scholar 

  2. Song Y, Li Z, Lin H, Du S, Hao Z, Lin H, et al. Effect of malondialdehyde treatment on the IgE binding capacity and conformational structure of shrimp tropomyosin. Food Chem. 2015;175:374–80.

    Article  CAS  Google Scholar 

  3. Sarici D, Gunes T, Yazici C, Akin MA, Korkmaz L, Memur S, et al. Investigation on malondialdehyde, S100B, and advanced oxidation protein product levels in significant hyperbilirubinemia and the effect of intensive phototherapy on these parameters. Pediatr Neonatol. 2015;56(2):95–100.

    Article  Google Scholar 

  4. Fujioka K, Shibamoto T. Improved malonaldehyde assay using headspace solid-phase microextraction and its application to the measurement of the antioxidant activity of phytochemicals. J Agric Food Chem. 2005;53(12):4708–13.

    Article  CAS  Google Scholar 

  5. Lim P, Wuenschell GE, Holland V, Lee DH, Pfeifer GP, Rodriguez H, et al. Peroxyl radical mediated oxidative DNA base damage: implications for lipid peroxidation induced mutagenesis. Biochemistry. 2004;43(49):15339–48.

    Article  CAS  Google Scholar 

  6. Shibamoto T. A novel gas chromatographic method for determination of malondialdehyde from oxidized DNA, in advanced protocols in oxidative stress III: Volume 1208 of the series methods in molecular biology. Springer, New York; 2015. p. 49–62.

  7. Chen JL, Huang YJ, Pan CH, Hu CW, Chao MR. Determination of urinary malondialdehyde by isotope dilution LC-MS/MS with automated solid-phase extraction: a cautionary note on derivatization optimization. Free Radic Biol Med. 2011;51(9):1823–9.

    Article  CAS  Google Scholar 

  8. Li P, Ding G, Deng Y, Punyapitak D, Li D, Cao Y. Determination of malondialdehyde in biological fluids by high-performance liquid chromatography using rhodamine B hydrazide as the derivatization reagent. Free Radic Biol Med. 2013;65:224–31.

    Article  CAS  Google Scholar 

  9. Faizan M, Esatbeyoglu T, Bayram B, Rimbach G. A fast and validated method for the determination of malondialdehyde in fish liver using high-performance liquid chromatography with a photodiode array detector. J Food Sci. 2014;79(4):C484–8.

    Article  CAS  Google Scholar 

  10. Hannan PA, Khan JA, Iqbal Z, Ullah I, Rehman WU, Rehman M, et al. Simultaneous determination of endogenous antioxidants and malondialdehyde by RP-HPLC coupled with electrochemical detector in serum samples. J Liq Chromatogr Relat Technol. 2015;38(10):1052–60.

    Article  Google Scholar 

  11. Ma B, Villalta PW, Balbo S, Stepanov I. Analysis of a malondialdehyde-deoxyguanosine adduct in human leukocyte DNA by liquid chromatography nanoelectrospray-high-resolution tandem mass spectrometry. Chem Res Toxicol. 2014;27(10):1829–36.

    Article  CAS  Google Scholar 

  12. Haller E, Lindner W, Lämmerhofer M. Gold nanoparticle-antibody conjugates for specific extraction and subsequent analysis by liquid chromatography-tandem mass spectrometry of malondialdehyde-modified low density lipoprotein as biomarker for cardiovascular risk. Anal Chim Acta. 2015;857:53–63.

    Article  CAS  Google Scholar 

  13. Al-Rimawi F. Development and validation of a simple reversed-phase HPLC-UV method for determination of malondialdehyde in olive oil. J Am Oil Chem Soc. 2015;92(7):933–7.

    Article  CAS  Google Scholar 

  14. Yahyavi H, Kaykhaii M, Hashemi M. A rapid spectrofluorimetric method for the determination of malondialdehyde in human plasma after its derivatization with thiobarbituric acid and vortex assisted liquid–liquid microextraction. RSC Adv. 2016;6(3):2361–7.

    Article  CAS  Google Scholar 

  15. Shin HS. Determination of malondialdehyde in human blood by headspace-solid phase micro-extraction gas chromatography–mass spectrometry after derivatization with 2,2,2-trifluoroethylhydrazine. J Chromatogr B Anal Technol Biomed Life Sci. 2009;877(29):3707–11.

    Article  CAS  Google Scholar 

  16. Bakalova R, Mileva M, Kotsev C, Bardarov V, Ribarov S. Determination of malondialdehyde in biological samples by solid-phase extraction and high-performance liquid chromatography. Methods Find Exp Clin Pharmacol. 2000;22(5):267–9.

    Article  CAS  Google Scholar 

  17. Novoselov KS, Geim AK, Morozov SV, Jiang D, Zhang Y, Dubonos SV, et al. Electric field in atomically thin carbon films. Science. 2004;306(5696):666–9.

    Article  CAS  Google Scholar 

  18. Liu Q, Shi J, Zeng L, Wang T, Cai Y, Jiang G. Evaluation of graphene as an advantageous adsorbent for solid-phase extraction with chlorophenols as model analytes. J Chromatogr A. 2011;1218(2):197–204.

    Article  CAS  Google Scholar 

  19. Li C, Lu A, Wang J, Li J, Ping H, Luan Y, et al. Determination of five sulfonylurea herbicides in environmental waters and soil by ultra high performance liquid chromatography with tandem mass spectrometry after extraction using graphene. J Sep Sci. 2014;37(24):3714–21.

    Article  CAS  Google Scholar 

  20. Shen Q, Gong L, Baibado JT, Dong W, Wang Y, Dai Z, et al. Graphene based pipette tip solid phase extraction of marine toxins in shellfish muscle followed by UPLC–MS/MS analysis. Talanta. 2013;116:770–5.

    Article  CAS  Google Scholar 

  21. Kumazawa T, Hasegawa C, Lee XP, Hara K, Seno H, Suzuki O, et al. Simultaneous determination of methamphetamine and amphetamine in human urine using pipette tip solid-phase extraction and gas chromatography–mass spectrometry. J Pharm Biomed Anal. 2007;44(2):602–7.

    Article  CAS  Google Scholar 

  22. Liu S, Yan H, Wang M, Wang L. Water-compatible molecularly imprinted microspheres in pipette tip solid-phase extraction for simultaneous determination of five fluoroquinolones in eggs. J Agric Food Chem. 2013;61(49):11974–80.

    Article  CAS  Google Scholar 

  23. Tsaknis J, Lalas S, Evmorfopoulos E. Determination of malondialdehyde in traditional fish products by HPLC. Analyst. 1999;124(6):843–5.

    Article  CAS  Google Scholar 

  24. Hummers Jr WS, Offeman RE. Preparation of graphitic oxide. J Am Chem Soc. 1958;80(6):1339.

    Article  CAS  Google Scholar 

  25. Metin Ö, Aydoğan Ş, Meral K. A new route for the synthesis of graphene oxide nanocomposites and their Schottky diode applications. J Alloy Compd. 2014;585:681–8.

    Article  CAS  Google Scholar 

  26. Sun H, Liu S, Zhou G, Ang HM, Tade MO, Wang S. Reduced graphene oxide for catalytic oxidation of aqueous organic pollutants. ACS Appl Mater Interfaces. 2012;4(10):5466–71.

    Article  CAS  Google Scholar 

  27. Titelman GI, Gelman V, Bron S, Khalfin RL, Cohen Y, Bianco-Peled H. Characteristics and microstructure of aqueous colloidal dispersions of graphite oxide. Carbon. 2005;43(3):641–9.

    Article  CAS  Google Scholar 

  28. Zhou Q, Fang Z. Graphene-modified TiO 2 nanotube arrays as an adsorbent in micro-solid phase extraction for determination of carbamate pesticides in water samples. Anal Chim Acta. 2015;869:43–9.

    Article  CAS  Google Scholar 

  29. Gioti EM, Fiamegos YC, Skalkos DC, Stalikas CD. Improved method for the in vitro assessment of antioxidant activity of plant extracts by headspace solid-phase microextraction and gas chromatography-electron capture detection. J Chromatogr A. 2007;1152(1–2):150–5.

    Article  CAS  Google Scholar 

  30. Wong S, Knight J, Hopfer S, Zaharia O, Leach CN, Sunderman F. Lipoperoxides in plasma as measured by liquid-chromatographic separation of malondialdehyde-thiobarbituric acid adduct. Clin Chem. 1987;33(2):214–20.

    CAS  Google Scholar 

  31. Kaykhaii M, Ghalehno MH. Rapid and sensitive determination of fluoride in toothpaste and water samples using headspace single drop microextraction-gas chromatography. Anal Methods. 2013;5(20):5622–6.

    Article  CAS  Google Scholar 

  32. Charoenpornpukdee K, Thammakhet C, Thavarungkul P, Kanatharana P. Novel pipette-tip graphene/poly (vinyl alcohol) cryogel composite extractor for the analysis of carbofuran and carbaryl in water. J Environ Sci Health B. 2014;49(10):713–21.

    Article  CAS  Google Scholar 

  33. Munoz AHS, Puga MP, Wrobel K, Sevilla MEG, Wrobel K. Micro assay for malondialdehyde in human serum by extraction-spectrophotometry using an internal standard. Microchim Acta. 2004;148(3–4):285–91.

    Article  CAS  Google Scholar 

  34. Suttnar J, Cermak J, Dyr JE. Solid-phase extraction in malondialdehyde analysis. Anal Biochem. 1997;249(1):20–3.

    Article  CAS  Google Scholar 

  35. Del Rio D, Pellegrini N, Colombi B, Bianchi M, Serafini M, Torta F, et al. Rapid fluorimetric method to detect total plasma malondialdehyde with mild derivatization conditions. Clin Chem. 2003;49(4):690–2.

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, Faculty of Sciences, University of Sistan and Baluchestan, Zahedan, 98135-674, Iran

    Massoud Kaykhaii & Hossain Yahyavi

  2. Department of Clinical Biochemistry, Cellular Molecular Research Centre, Zahedan University of Medical Sciences, Zahedan, 98167-431758, Iran

    Mohammad Hashemi

  3. Department of Chemistry, Faculty of Science, University of Zanjan, Zanjan, 45371-38791, Iran

    Mohammad Reza Khoshroo

Authors
  1. Massoud Kaykhaii
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Hossain Yahyavi
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Mohammad Hashemi
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Mohammad Reza Khoshroo
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Massoud Kaykhaii.

Ethics declarations

All experiments with human plasma were also performed in compliance with the relevant laws in Iran and institutional guidelines, and relevant ethical committees in Zahedan University of Medical Sciences and The University of Sistan and Baluchestan have approved the experiments. Consent was obtained for any experimentation with human subjects.

Conflict of interest

The authors state that they have no conflicts of interest.

Electronic supplementary material

Below is the link to the electronic supplementary material.

ESM 1

(PDF 34 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Kaykhaii, M., Yahyavi, H., Hashemi, M. et al. A simple graphene-based pipette tip solid-phase extraction of malondialdehyde from human plasma and its determination by spectrofluorometry. Anal Bioanal Chem 408, 4907–4915 (2016). https://doi.org/10.1007/s00216-016-9577-x

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-016-9577-x

Keywords

Search

Navigation