title: Esters of 3-chloro-1,2-propanediol (3-MCPD) in vegetable oils: significance in the formation of 3-MCPD.
abstract: 3-Mono-chloropropane-1,2-diol (3-MCPD) is a contaminant that occurs in food in its free (diol) form as well as in an esterified (with fatty acids) form. Using a simple intestinal model, it was demonstrated that 3-MCPD monoesters and 3-MCPD diesters are accepted by intestinal lipase as substrates in vitro. Under the chosen conditions, the yield of 3-MCPD from a 3-MCPD monoester was greater than 95% in approximately 1 min. Release from the diesters was slower, reaching about 45, 65 and 95% of 3-MCPD after 1, 5 and 90 min of incubation, respectively. However, in human, the hydrolysis of 3-MCPD esters is unlikely to release 100% as 3-MCPD, as triglycerides and phospholipids are hydrolysed in the intestine liberating 2-monoglycerides. Assuming a similar metabolism for 3-MCPD esters as that known for acylglycerols in humans in vivo, the de-esterification in positions 1 and 3 would thus be favoured by pancreatic lipases. Therefore, 3-MCPD, and 3-MCPD-2 monoesters would be released, respectively, from the 1-/3-monoesters, and the diesters potentially present in food. Hence, information on the exact amounts of the partial fatty acid chloroesters, i.e. 3-MCPD mono- and diesters, is important to assess the contribution of foods to the bioavailability of 3-MCPD. Therefore, a rapid method for the determination of the ratio of 3-MCPD monoesters to diesters in fats and oils was developed using gas chromatography-mass spectrometry (GC-MS) and isotopically labelled 3-MCPD esters as internal standards. The analysis of 11 different samples of fat mixes typically employed in food manufacturing demonstrated that a maximum of about 15% of the total amount of 3-MCPD bound in esters is present in the monoesterified form. The potentially slower release of 3-MCPD from 3-MCPD diesters, and the mono- to diesters ratio suggest that 3-MCPD esters may in fact contribute only marginally to the overall dietary exposure to 3-MCPD. Further work on the bioavailability, metabolism and possible toxicity of chloroesters per se is warranted.
authors.affiliation: Quality and Safety Assurance Department, Nestlé Research Center, Nestec Ltd, CH-1000 Lausanne 26, Switzerland. walburga.seefelder@rdls.nestle.com
authors.forename: W
authors.initials: W
authors.lastname: Seefelder
authors.forename: N
authors.initials: N
authors.lastname: Varga
authors.forename: A
authors.initials: A
authors.lastname: Studer
authors.forename: G
authors.initials: G
authors.lastname: Williamson
authors.forename: F P
authors.initials: FP
authors.lastname: Scanlan
authors.forename: R H
authors.initials: RH
authors.lastname: Stadler
mesh_terms: D000818:Animals; D001646:Bile / Q000737:chemistry; D001647:Bile Acids and Salts / Q000378:metabolism; D001682:Biological Availability; D004952:Esters / Q000378:metabolism; D005227:Fatty Acids / Q000378:metabolism; D005504:Food Analysis / Q000379:methods*; D005506:Food Contamination / Q000032:analysis*; D008401:Gas Chromatography-Mass Spectrometry; D006801:Humans; D006868:Hydrolysis; D008049:Lipase / Q000037:antagonists & inhibitors / Q000378:metabolism; D008066:Lipolysis; D009682:Magnetic Resonance Spectroscopy; D010194:Pancreatin / Q000378:metabolism; D010938:Plant Oils / Q000737:chemistry*; D015203:Reproducibility of Results; D013379:Substrate Specificity; D013552:Swine; D000517:alpha-Chlorohydrin / Q000032:analysis / Q000737:chemistry / Q000378:metabolism*
chemical_list: D001647:Bile Acids and Salts; D004952:Esters; D005227:Fatty Acids; D010938:Plant Oils; D010194:Pancreatin; D000517:alpha-Chlorohydrin; D008049:Lipase