Skip to main content
SpringerLink
Log in

Determination of free apocarotenoids and apocarotenoid esters in human colostrum

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

Abstract

The presence of carotenoids in human colostrum has been reported in the literature, and xanthophyll esters in human colostrum were recently detected for the first time. However, no published studies have reported whether apocarotenoids, which are metabolites derived from carotenoid enzymatic or nonenzymatic oxidative cleavage, are present in human colostrum. Therefore, the purpose of the present study was to search for the possible occurrence of apocarotenoids, including apocarotenoid esters, in human colostrum for the first time by applying an online supercritical fluid extraction–supercritical fluid chromatography–tandem mass spectrometry methodology. Recent evidence related to apocarotenoid transcriptional activity has suggested that they may have beneficial health properties superior to those of their parent carotenoids. Three different apocarotenoids, namely apo-8′-β-carotenal, apo-8′-lycopenal, and β-citraurin, were identified in intact human colostrum samples, with average concentrations of 85 nmol L−1, 54.6 nmol L−1, and 75.4 nmol L−1, respectively. The overall detection of 16 different free apocarotenoids and 10 different apocarotenoid fatty acid esters in human colostrum was achieved here for the first time. Their occurrence in human colostrum certainly has implications for newborn health status, since colostrum is the only form of food for the newborn during the very first days of life.

Graphical abstract

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

Similar content being viewed by others

Abbreviations

APCI:

Atmospheric pressure chemical ionization

MS:

Mass spectrometry

QqQ:

Triple quadrupole

SFC:

Supercritical fluid chromatography

SFE:

Supercritical fluid extraction

References

  1. Harrison EH, Quadro L. Apocarotenoids: emerging roles in mammals. Annu Rev Nutr. 2018;38:153–72.

    Article  CAS  Google Scholar 

  2. Shete V, Quadro L. Mammalian metabolism of β-carotene: gaps in knowledge. Nutrients. 2013;5:4849–68.

    Article  CAS  Google Scholar 

  3. Eroglu A, Harrison EH. Carotenoid metabolism in mammals, including man: formation, occurrence, and function of apocarotenoids. J Lipid Res. 2013;54:1719–30.

    Article  CAS  Google Scholar 

  4. Meléndez-Martìnez AJ. An overview of carotenoids, apocarotenoids, and vitamin a in agro-food, nutrition, health, and disease. Mol Nutr Food Res. 2019;63:1801045.

    Article  Google Scholar 

  5. Giuffrida D, Donato P, Dugo P, Mondello L. Recent analytical techniques advances in the carotenoids and their derivatives determination in various matrixes. J Agric Food Chem. 2018;66:3302–7.

    Article  CAS  Google Scholar 

  6. Ma G, Zhang L, Matsuta A, Matsutani K, Yamawaki K, Yahata M, et al. Enzymatic formation of β-citraurin from β-cryptoxanthin and zeaxanthin by carotenoid cleavage dioxygenase4 in the flavedo of Citrus fruit. Plant Physiol. 2013;163:682–95.

    Article  CAS  Google Scholar 

  7. Hou X, Rivers J, Leòn P, McQuinn RP, Pogson BJ. Synthesis and function of apocarotenoid signals in plant. Trends Plant Sci. 2016;21(9):792–03.

    Article  CAS  Google Scholar 

  8. Zoccali M, Giuffrida D, Salafia F, Giofrè SV, Mondello L. Carotenoids and apocarotenoids determination in intact human blood samples by online supercritical fluid extraction-supercritical fluid chromatography-tandem mass spectrometry. Anal Chim Acta. 2018;1032:40–7.

    Article  CAS  Google Scholar 

  9. Xavier AAO, Dìaz-Salido E, Arenilla-Vélez I, Aguayo-Maldonado J, Garrido-Fernàndez J, Fonteca J, Sànches-Garcìa A, Pérez-Gàlvez A. Carotenoid content in human colostrum is associated to preterm/full-term birth condition. Nutrients 2018; 10: Art.1654.

    Article  Google Scholar 

  10. Xue Y, Campos-Giménez E, Redeuil KM, Léveques A, Actis-Goretta L, Vinyes-Pares G, Zhang Y, Wang P, Thakkar SK. Concentrations of carotenoids and tocopherols in breast milk from urban Chinese mothers and their associations with maternal characteristics: A cross-sectional study. Nutrients 2017; 9: Art.1229.

    Article  Google Scholar 

  11. Schweigert FJ, Bathe K, Chen F, Buscher U, Dudenhausen JW. Effect of the stage of lactation in humans on carotenoid levels in milk, blood plasma and plasma lipoprotein fractions. Eur J Nutr. 2004;43:30–44.

    Article  Google Scholar 

  12. Macias C, Schweigert FJ. Changes in the concentration of carotenoids, vitamin a, alpha-tocopherol and total lipids in human milk throughout early lactation. Ann Nutr Metab. 2001;45:82–5.

    Article  CAS  Google Scholar 

  13. Patton S, Canfield LM, Huston GE, Ferris AM, Jensen RG. Carotenoids in human colostrum. Lipids 1990; 25: Art. 159.

    Article  CAS  Google Scholar 

  14. Rios JJ, Xavier AAO, Dìaz-Salido E, Arenilla-Vélez I, Jarén-Galàn M, Garrido-Fernàndez J, Aguayo-Maldonado J, Pérez-Gàlvez A. Xanthophyll esters are found in human colostrum. Mol Nutr Food Res. 2017; 61(10): Art.1700296.

    Article  Google Scholar 

  15. Rodriguez EB, Rodriguez-Amaya DB. Formation of apocarotenals and epoxycarotenoids from β-carotene by chemical reactions and by autoxidation in model system and processed foods. Food Chem. 2007;101:563–72.

    Article  CAS  Google Scholar 

  16. Giuffrida D, Zoccali M, Giofrè SV, Dugo P, Mondello L. Apocarotenoids determination in Capsicum chinense Jacq. cv habanero, by supercritical fluid chromatography-mass spectrometry. Food Chem. 2017;231:316–23.

    Article  CAS  Google Scholar 

  17. Zoccali M, Giuffrida D, Dugo P, Mondello L. Direct online extraction and determination by supercritical fluid extraction with chromatography and mass spectrometry of targeted carotenoids from Habanero peppers (Capsicum chinense Jacq.). J Sep Sci. 2017;40:3905–13.

    Article  CAS  Google Scholar 

  18. Zoccali M, Donato P, Mondello L. Recent advances in the coupling of carbon dioxide-based extraction and separation techniques. Trac-Trend Anal Chem. 2019;116:158–65.

    Article  CAS  Google Scholar 

  19. van Breemen RB, Schmitz HH, Schwartz SJ. Fast atom bombardment tandem mass spectrometry of carotenoids. J Agric Food Chem. 1995;43:384–9.

    Article  Google Scholar 

  20. Mordi RC, Waton JC. Identification of products from canthaxanthin oxidation. Food Chem. 2016;197:836–40.

    Article  CAS  Google Scholar 

  21. Fleshman MK, Lester GE, Riedl KM, Kopec RE, Narayanasamy S, Curley RW, et al. Carotene and novel apocarotenoid concentrations in orange-fleshed Cucumis melo melons: determinations of β-carotene bioaccessibility and bioavailability. J Agric Food Chem. 2011;59:4448–54.

    Article  CAS  Google Scholar 

  22. Kopec RE, Riedl KM, Harrison EH, Curley RW, Hruszkewycz DP, Clinton SK, et al. Identification and quantification of apo-lycopenals in fruits, vegetables and human plasma. J Agric Food Chem. 2010;58:3290–6.

    Article  CAS  Google Scholar 

  23. von Lintig J. Provitamin a metabolism and functions in mammalian biology. Am J Clin Nutr. 2012;96:1234S–44S.

    Article  Google Scholar 

  24. Hu KQ, Liu C, Ernst H, Krinsky NL, Russell RM, Wang XD. The biochemical characterization of ferret carotene-9′-10′-monooxygenase catalyzing cleavage of carotenoids in vitro and in vivo. J Biol Chem. 2006;281:19327–32.

    Article  CAS  Google Scholar 

  25. Mein JR, Lian F, Wang XD. Biological activity of lycopene metabolites: implications for cancer prevenction 2008; 66(12): 667–83.

  26. Carotenoid Esters in Foods: Physical, Chemical and Biological Properties. Edited by Adriana Z. Mercadante. The Royal Society of Chemistry, 2019.

Download references

Acknowledgements

We gratefully acknowledge Shimadzu and Merck KGaA for their continuous support.

Author information

Authors and Affiliations

  1. Department of Mathematical and Computer Science, Physical Sciences and Earth Sciences, University of Messina, 98122, Messina, Italy

    Mariosimone Zoccali

  2. Dipartimento di Scienze Biomediche, Odontoiatriche e delle Immagini Morfologiche e Funzionali, University of Messina, Via Consolare Valeria, 98125, Messina, Italy

    Daniele Giuffrida

  3. Department of Human Pathology in Adult and Childhood “G. Barresi”, University of Messina, Via Consolare Valeria, 98125, Messina, Italy

    Roberta Granese

  4. Dipartimento di Scienze Chimiche, Biologiche, Farmaceutiche ed Ambientali, University of Messina, Polo Annunziata - Viale Annunziata, 98168, Messina, Italy

    Fabio Salafia, Paola Dugo & Luigi Mondello

  5. Chromaleont s.r.l., c/o Department of Chemical, Biological, Pharmaceutical and Environmental Sciences, University of Messina, 98168, Messina, Italy

    Paola Dugo & Luigi Mondello

  6. BeSep s.r.l., c/o Department of Chemical, Biological, Pharmaceutical and Environmental Sciences, University of Messina, 98168, Messina, Italy

    Paola Dugo & Luigi Mondello

  7. Unit of Food Science and Nutrition, Department of Medicine, University Campus Bio-Medico of Rome, 00128, Rome, Italy

    Paola Dugo & Luigi Mondello

Authors
  1. Mariosimone Zoccali
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Daniele Giuffrida
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Roberta Granese
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Fabio Salafia
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Paola Dugo
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Luigi Mondello
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Daniele Giuffrida.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Ethical standards

This study was carried out in compliance with ethical standards.

Sample collection was carried out at the Messina University Polyclinic Hospital, and although all participants were volunteers, they all provided written consent.

Additional information

Publisher’s note

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

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zoccali, M., Giuffrida, D., Granese, R. et al. Determination of free apocarotenoids and apocarotenoid esters in human colostrum. Anal Bioanal Chem 412, 1335–1342 (2020). https://doi.org/10.1007/s00216-019-02359-z

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-019-02359-z

Keywords

Search

Navigation