Skip to main content
Log in

A High-Resolution NMR Approach Combined to MALDI-TOF-MS to Estimate the Positional Distribution of Acyl-Linked Unsaturated Fatty Acids in Triacylglycerols

Food Analytical Methods Aims and scope Submit manuscript

Abstract

Triacylglycerols (TAGs) are the most abundant constituents of vegetable oils and adipose tissues. TAG analysis is even, nowadays, challenging because the presence of three (often different) fatty acyl residues leads to many different, regioisomeric species. While the overall fatty acyl composition of TAG can be determined by gas chromatography/mass spectrometry (GC/MS), all positional information is completely lost by this approach. Therefore, GC/MS is often replaced or combined with LC/MS that provides information (by MS/MS) which fatty acyl residues are present in a given TAG and sometimes also about the location at the glycerol backbone. Since TAGs are normally available in huge amounts, the comparably low sensitivity of NMR is not a major issue. We show that high-resolution 13C NMR spectroscopy is an excellent method to determine the overall fatty acyl composition and the positions of the related (unsaturated) fatty acyl residues in a given TAG molecule. These data will be compared with MALDI-TOF MS data of the same vegetable oil samples. Although the 13C NMR method is particularly applicable to unsaturated TAG, this approach can be regarded as a significant methodological progress in this field.

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

Access this article

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

References

  • Angulo J, Hiller B, Olivera M, Mahecha L, Dannenberger D, Nuernberg G, Losand B, Nuernberg K (2012) Dietary fatty acid intervention of lactating cows simultaneously affects lipid profiles of meat and milk. J Sci Food Agric 92:2968–2974

    Article  CAS  Google Scholar 

  • Barison A, Pereira da Silva CW, Campos FR, Simonelli F, Lenz CA, Ferreira AG (2010) A simple methodology for the determination of fatty acid composition in edible oils through 1H NMR spectroscopy. Magn Reson Chem 48:642–650

    CAS  Google Scholar 

  • Baud S, Lepiniec L (2010) Physiological and developmental regulation of seed oil production. Prog Lipid Res 49:235–249

    Article  CAS  Google Scholar 

  • Bono L, Seraglia R, Roverso M, Di Carro M, Magi E (2014) Triacylglycerol profile in cocoa liquors using MALDI-TOF and LC-ESI tandem mass spectrometry. J Mass Spectrom 49:894–899

    Article  CAS  Google Scholar 

  • Bosque-Sendra JM, Cuadros-Rodríguez L, Ruiz-Samblás C, de la Mata AP (2012) Combining chromatography and chemometrics for the characterization and authentication of fats and oils from triacylglycerol compositional data a review. Anal Chim Acta 724:1–11

    Article  CAS  Google Scholar 

  • Dannenberger D, Nuernberg K, Nuernberg G, Priepke A (2012) Different dietary protein and PUFA interventions alter the fatty acid concentrations, but not the meat quality, of porcine muscle. Nutrients 4:1237–1246

    Article  CAS  Google Scholar 

  • Delmonte P, Kia AR, Hu Q, Rader JI (2009) Review of methods for preparation and gas chromatographic separation of trans and cis reference fatty acids. J AOAC Int 92:1310–1326

    CAS  Google Scholar 

  • Fuchs B, Süss R, Schiller J (2010) An update of MALDI-TOF mass spectrometry in lipid research. Prog Lipid Res 49:450–475

    Article  CAS  Google Scholar 

  • Gidden J, Liyanage R, Durham B, Lay JO Jr (2007) Reducing fragmentation observed in the matrix-assisted laser desorption/ionization time-of-flight mass spectrometric analysis of triacylglycerols in vegetable oils. Rapid Commun Mass Spectrom 21:1951–1957

    Article  CAS  Google Scholar 

  • Griffiths WJ (2003) Tandem mass spectrometry in the study of fatty acids, bile acids, and steroids. Mass Spectrom Rev 22:81–152

    Article  CAS  Google Scholar 

  • Jakab A, Nagy K, Héberger K, Vékey K, Forgács E (2002) Differentiation of vegetable oils by mass spectrometry combined with statistical analysis. Rapid Commun Mass Spectrom 16:2291–2297

    Article  CAS  Google Scholar 

  • Lísa M, Netušilová K, Franěk L, Dvořáková H, Vrkoslav V, Holčapek M (2011) Characterization of fatty acid and triacylglycerol composition in animal fats using silver-ion and non-aqueous reversed-phase high-performance liquid chromatography/mass spectrometry and gas chromatography/flame ionization detection. J Chromatogr A 1218:7499–7510

    Article  Google Scholar 

  • Lísa M, Holčapek M (2013) Characterization of triacylglycerol enantiomers using chiral HPLC/APCI-MS and synthesis of enantiomeric triacylglycerols. Anal Chem 85:1852–1859

    Article  Google Scholar 

  • Mannina L, Luchinat C, Emanuele MC, Segre A (1999) Acyl positional distribution of glycerol tri-esters in vegetable oils: a 13C-NMR study. Chem Phys Lipids 103:47–55

    Article  CAS  Google Scholar 

  • Mannina L, Sobolev AP (2011) High resolution NMR characterization of olive oils in terms of quality, authenticity and geographical origin. Magn Reson Chem 49(Suppl 1):S3–11

    Article  CAS  Google Scholar 

  • Mavromoustakos T, Zervou M, Bonas G, Kolocouris A, Petrakis P (2000) A novel analytical method to detect adulteration of virgin olive oil by other oils. J Am Oil Chem Soc 77:405–411

    Article  CAS  Google Scholar 

  • Nalbone G, Leonardi J, Termine E, Portugal H, Lechene P, Pauli AM, Lafont H (1989) Effects of fish oil, corn oil and lard diets on lipid peroxidation status and glutathione peroxidase activities in rat heart. Lipids 24:179–186

    Article  CAS  Google Scholar 

  • Pollesello P, Eriksson O, Hockerstedt K (1996) Analysis of total lipid extracts from human liver by 13C and 1H nuclear magnetic resonance spectroscopy. Anal Biochem 236:41–48

    Article  CAS  Google Scholar 

  • Popkova Y, Meusel A, Breitfeld J, Schleinitz D, Hirrlinger J, Dannenberger D, Kovacs P, Schiller J (2015) Nutrition-dependent changes of mouse adipose tissue compositions monitored by NMR, MS, and chromatographic methods. Anal Bioanal Chem 407:5113–5123

    Article  CAS  Google Scholar 

  • Šala M, Lísa M, Campbell JL, Holčapek M (2016) Determination of triacylglycerol regioisomers using differential mobility spectrometry. Rapid Commun Mass Spectrom 30:256–264

    Article  Google Scholar 

  • Schiller J, Arnhold J, Benard S, Müller M, Reichl S, Arnold K (1999) Lipid analysis by matrix-assisted laser desorption and ionization mass spectrometry: a methodological approach. Anal Biochem 267:46–56

    Article  CAS  Google Scholar 

  • Schiller J, Süss R, Petković M, Hilbert N, Müller M, Zschörnig O, Arnhold J, Arnold K (2001) CsCl as an auxiliary reagent for the analysis of phosphatidylcholine mixtures by matrix-assisted laser desorption and ionization time-of-flight mass spectrometry (MALDI-TOF MS). Chem Phys Lipids 113:123–131

    Article  CAS  Google Scholar 

  • Schiller J, Süß R, Petković M, Hanke G, Vogel A, Arnold K (2002a) Effects of thermal stressing on saturated vegetable oils and isolated triacylglycerols—product analysis by MALDI-TOF mass spectrometry, NMR and IR spectroscopy. Eur J Lipid Sci Technol 104:496–505

    Article  CAS  Google Scholar 

  • Schiller J, Süß R, Petković M, Arnold K (2002b) Triacylglycerol analysis of vegetable oils by matrix-assisted laser desorption and ionization time-of-flight (MALDI-TOF) mass spectrometry and 31P NMR spectroscopy. J Food Lipids 9:185–200

    Article  CAS  Google Scholar 

  • Vigli G, Philippidis A, Spyros A, Dais P (2003) Classification of edible oils by employing 31P and 1H NMR spectroscopy in combination with multivariate statistical analysis. A proposal for the detection of seed oil adulteration in virgin olive oils. J Agric Food Chem 51:5715–5722

    Article  CAS  Google Scholar 

  • Vlahov G, Shaw AD, Kell DB (1999) Use of 13C nuclear magnetic resonance distortionless enhancement by polarization transfer pulse sequence and multivariate analysis to discriminate olive oil cultivars. J Am Oil Chem Soc 76:1223–1231

    Article  CAS  Google Scholar 

  • Wiener M, Rothkopf MM, Rothkopf G, Askanazi J (1987) Fat metabolism in injury and stress. Crit Care Clin 3:25–56

    CAS  Google Scholar 

  • Zamora R, Alba V, Hidalgo FJ (2001) Use of high-resolution 13C nuclear magnetic resonance spectroscopy for the screening of virgin olive oils. J Am Oil Chem Soc 78:89–94

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This study was supported by the German Research Council (DFG Schi 476/12-2 and Schi 476/16-1 and SFB 1052/Z3). We would also like to thank all our colleagues who helped us in performing the related experiments. We are particularly indebted to Bruker Daltonics (Bremen) and Merck Millipore (Darmstadt) for the continuous and generous support.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Jürgen Schiller.

Ethics declarations

Funding

This study was funded by the German Research Council (in particular, grant number SFB 1052/B6).

Conflict of Interest

Andrej Meusel declares that he has no conflict of interest. Yulia Popkova declares that she has no conflict of interest. Dirk Dannenberger declares that he has no conflict of interest. Jürgen Schiller declares that he has no conflict of interest.

Ethical Approval

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

Informed Consent

Not applicable.

Electronic Supplementary Material

Supplementary Table 1

(DOCX 31 kb)

Supplementary Fig. 1

150.92 MHz 13C NMR spectrum of 10% solution of trilinolenin in CDCl3/MeOD (2:1, v/v) using a common 5 mm probe.(GIF 15 kb)

High Resolution (EPS 243 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Meusel, A., Popkova, Y., Dannenberger, D. et al. A High-Resolution NMR Approach Combined to MALDI-TOF-MS to Estimate the Positional Distribution of Acyl-Linked Unsaturated Fatty Acids in Triacylglycerols. Food Anal. Methods 10, 2497–2506 (2017). https://doi.org/10.1007/s12161-017-0818-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s12161-017-0818-1

Keywords

Navigation