Abstract
An analytical method suitable for the determination of 4-hydroxy-2-(E)-nonenal (HNE) and 4-hydroxy-2-(E)-hexenal (HHE) in various food matrices was developed and validated. The method involves the use of deuterated HNE and HHE as internal standards, extraction of the analytes from the matrices followed by derivatization and detection with gas chromatography–mass spectrometry. Four different food matrices were chosen as model systems including vegetable oils, unprocessed meat, fried potato crisps, and infant formula and three different extraction techniques suitable for the different matrices were applied including the Quick Easy Cheap Effective Rugged Safe method. The simplicity of the extraction techniques allows the method to be applied for routine analysis of a large amount of samples. The results verify the accuracy and reproducibility of the analytical technique and its ability to provide reliable quantification of both analytes at concentrations as low as 12.8 ng g−1 in meat samples. Furthermore, a short overview of the levels of HNE and HHE in several products available in the Belgian market is presented.
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Anastassiades M, Lehotay SJ, Stajnbaher D, Schenck FJ (2003) Fast and easy multiresidue method employing acetonitrile extraction/partitioning and “dispersive solid-phase extraction” for the determination of pesticide residues in produce. J AOAC Int 86:412–431
Belitz HD, Grosh W, Schieberle P (2009) Food chemistry. Springer, Berlin
Esterbauer H (1982) Lipid peroxidation and cancer. In: Esterbauer H (ed) Free radicals. Academic, London, pp 101–128
Esterbauer H, Schaur RJ, Zollner H (1991) Chemistry and biochemistry of 4-hydroxynonenal, malonaldehyde and related aldehydes. Free Radic Biol Med 11:81–128
European Community (2002) European Union: Commission Decision 2002/657/EC implementing Council Directive 96/23/EC concerning the performance of analytical methods and the interpretation of results. Official Journal of the European Communities L221, pp. 8–36
Goicoechea E, Van Twillert K, Duits M, Brandon ED, Kootstra PR, Blokland MH, Guillen MD (2008) Use of an in vitro digestion model to study the bioaccessibility of 4-hydroxy-2-nonenal and related aldehydes present in oxidized oils rich in omega-6 acyl groups. J Agric Food Chem 56:8475–8483
Goicoechea E, Brandon EF, Blokland MH, Guillen MD (2011) Fate in digestion in vitro of several food components, including some toxic compounds coming from omega-3 and omega-6 lipids. Food Chem Toxicol 49:115–124
Guillen MD, Goicoechea E (2008a) Toxic oxygenated alpha, beta-unsaturated aldehydes and their study in foods: a review. Crit Rev Food Sci Nutr 48:119–136
Guillen MD, Goicoechea E (2008b) Formation of oxygenated alpha, beta-unsaturated aldehydes and other toxic compounds in sunflower oil oxidation at room temperature in closed receptacles. Food Chem 111:157–164
Guillen MD, Uriarte PS (2012) Aldehydes contained in edible oils of a very different nature after prolonged heating at frying temperature: presence of toxic oxygenated alpha, beta unsaturated aldehydes. Food Chem 131:915–926
Guillen MD, Carton I, Salmeron J, Casas C (2009) Headspace composition of cod liver oil and its evolution in storage after opening. First evidence of the presence of toxic aldehydes. Food Chem 114:1291–1300
Han IH, Csallany AS (2009) Formation of toxic alpha, beta-unsaturated 4-hydroxy-aldehydes in thermally oxidized fatty acid methyl esters. J Am Oil Chem Soc 86:253–260
Han IH, Csallany A (2012) The toxic aldehyde, 4-hydroxy-2-trans-nonenal (HNE) formation in natural and imitation mozzarella cheeses: heat treatment effects. J Am Oil Chem Soc 89:1801–1805
Kinter M (1995) Analytical technologies for lipid oxidation-products analysis. J Chromatogr B-Biomed Appl 671:223–236
LaFond SI, Jerrell JP, Cadwallader KR, Artz WE (2011) Formation of 4-hydroxy-2-(E)-nonenal in a corn-soy oil blend: a controlled heating study using a French fried potato model. J Am Oil Chem Soc 88:763–772
Long EK, Picklo S (2010) Trans-4-hydroxy-2-hexenal, a product of n-3 fatty acid peroxidation: make some room HNE. Free Radic Biol Med 49:1–8
Michalski MC, Calzada C, Makino A, Michaud S, Guichardant M (2008) Oxidation products of polyunsaturated fatty acids in infant formulas compared to human milk—a preliminary study. Mol Nutr Food Res 52:1478–1485
Mocak J, Bond AM, Mitchell S, Scollary G (1997) A statistical overview of standard (IUPAC and ACS) and new procedures for determining the limits of detection and quantification: application to voltammetric and stripping techniques (technical report). Pure Appl Chem 69:297–328
Naveena B, Faustman C, Tatiyaborworntham N, Yin S, Ramanathan R, Mancini R (2010) Detection of 4-hydroxy-2-nonenal adducts of turkey and chicken myoglobins using mass spectrometry. Food Chem 122:836–840
Payà P, Anastassiades M, Mack D, Sigalova I, Tasdelen B, Oliva J, Barba A (2007) Analysis of pesticide residues using the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) pesticide multiresidue method in combination with gas and liquid chromatography and tandem mass spectrometric detection. Anal Bioanal Chem 389:1697–1714
Pryor WA, Porter NA (1990) Suggested mechanisms for the production of 4-hydroxy-2-nonenal from the autoxidation of polyunsaturated fatty-acids. Free Radic Biol Med 8:541–543
Rauniyar N, Prokai L (2009) Detection and identification of 4-hydroxy-2-nonenal Schiff-base adducts along with products of Michael addition using data-dependent neutral loss-driven MS3 acquisition: method evaluation through an in vitro study on cytochrome c oxidase modifications. Proteomics 9:5188–5193
Rees MS, Vankuijk FJGM, Siakotos AN, Mundy BP (1995) Improved synthesis of various isotope labeled 4-hydroxyalkenals and peroxidation intermediates. Synth Commun 25:3225–3236
Santaniello E, Repetto A, Chiesa LM, Biondi PA (2007) Synthesis and characterization of 4-hydroxy-2-nonenal derivatives for gas chromatographic analysis with electron capture detection (GC-ECD). Redox Rep 12:55–58
Seppanen CM, Csallany AS (2001) Simultaneous determination of lipophilic aldehydes by high-performance liquid chromatography in vegetable oil. J Am Oil Chem Soc 78:1253–1260
Seppanen CM, Csallany AS (2002) Formation of 4-hydroxynonenal, a toxic aldehyde, in soybean oil at frying temperature. J Am Oil Chem Soc 79:1033–1038
StAngelo AJ (1996) Lipid oxidation in foods. Crit Rev Food Sci Nutr 36:175–224
Surh J, Kwon H (2002) Quantitation of 4-hydroxyalkenals in oils consumed in Korea. Abstr Pap Am Chem Soc 224:U76
Surh J, Kwon H (2003) Simultaneous determination of 4-hydroxy-2-alkenals, lipid peroxidation toxic products. Food Addit Contam 20:325–330
Surh J, Kwon H (2005) Estimation of daily exposure to 4-hydroxy-2-alkenals in Korean foods containing n-3 and n-6 polyunsaturated fatty acids. Food Addit Contam 22:701–708
Surh J, Lee S, Kwon H (2007) 4-Hydroxy-2-alkenals in polyunsaturated fatty acids-fortified infant formulas and other commercial food products. Food Addit Contam 24:1209–1218
Surh J, Lee BY, Kwon H (2010) Influence of fatty acids compositions and manufacturing type on the formation of 4-hydroxy-2-alkenals in food lipids. Food Sci Biotechnol 19:297–303
Uchida K, Stadtman ER (1992) Modification of histidine-residues in proteins by reaction with 4-hydroxynonenal. Proc Natl Acad Sci U S A 89:4544–4548
Vankuijk FJGM, Siakotos AN, Fong LG, Stephens RJ, Thomas DW (1995) Quantitative measurement of 4-hydroxyalkenals in oxidized low-density lipoprotein by gas chromatography–mass spectrometry. Anal Biochem 224:420–424
Voulgaridou GP, Anestopoulos I, Franco R, Panayiotidis MI, Pappa A (2011) DNA damage induced by endogenous aldehydes: current state of knowledge. Mutat Res Fundam Mol Mech Mutagen 711:13–27
Zanardi E, Jagersma CG, Ghidini S, Chizzolini R (2002) Solid phase extraction and liquid chromatography-tandem mass spectrometry for the evaluation of 4-hydroxy-2-nonenal in pork products. J Agric Food Chem 50:5268–5272
Acknowledgments
The authors gratefully acknowledge the Federal Public Service of Health, Food Chain Safety and Environment (project RT/10 TOXAL) for funding this research.
Compliance with Ethics Requirements
Antonios Papastergiadis has received a research grant from the Belgian Federal Public Service of Health.
Conflict of Interest
Edward Mubiru does not have a conflict of interest. Herman Van Langenhove does not have a conflict of interest. Bruno De Meulenaer does not have a conflict of interest. This article does not contain any studies with human or animal subjects.
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Papastergiadis, A., Mubiru, E., Van Langenhove, H. et al. Development of a Sensitive and Accurate Stable Isotope Dilution Assay for the Simultaneous Determination of Free 4-Hydroxy-2-(E)-Nonenal and 4-Hydroxy-2-(E)-Hexenal in Various Food Matrices by Gas Chromatography–Mass Spectrometry. Food Anal. Methods 7, 836–843 (2014). https://doi.org/10.1007/s12161-013-9689-2
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DOI: https://doi.org/10.1007/s12161-013-9689-2