title: Regiospecific determination of short-chain triacylglycerols in butterfat by normal-phase HPLC with on-line electrospray-tandem mass spectrometry.
abstract: This study uses normal-phase HPLC with on-line positive ion electrospray mass spectrometry (ESI-MS) to obtain quantitative compositional data on both synthetic and butterfat short-chain TAG. The product ion tandem MS of standards averaged 11.1 times lower in abundance of the ion formed by cleavage of FA from the sn-2-position for the pairs of regioisomers in the TAG classes: L/L/S-L/S/L and L/S/S-S/L/S, where L denotes long and S short acyl chain (C2-C6). The molar correction factors, determined for 42 regioisomeric pairs of short-chain TAG of 20 randomized mixture of standards, differed by 1.4-80% as the ratios varied between 0.217 and 5.847. Butterfat TAG were resolved into four fractions on short flash chromatography grade silica gel columns. Pairs of regioisomers in the TAG classes L/S/S-S/L/S with predominance of L/S/S isomers and the sole regioisomers in the TAG classes L/L(M)/S were identified by tandem MS, where M denotes either 8:0 or 10:0 acyl chain. The total proportion of L/L(M)/S isomers was estimated at 34.7 and that of L/S/S-S/L/S at 1.0 mol%, including a small proportion of S/S/S. In contrast to previous work, the present data indicate the presence of a small proportion of butyric and caproic acids in the sn-1-position. The overall distribution of the FA in the short-chain TAG of butterfat, calculated from direct MS measurements, was consistent with the results of indirect determinations based on stereospecific analyses of total butterfat.
authors.affiliation: Department of Applied Chemistry and Microbiology, University of Helsinki, Helsinki, Finland. Paavo.Kalo@Helsinki.Fi
authors.forename: P
authors.initials: P
authors.lastname: Kalo
authors.forename: A
authors.initials: A
authors.lastname: Kemppinen
authors.forename: V
authors.initials: V
authors.lastname: Ollilainen
authors.forename: A
authors.initials: A
authors.lastname: Kuksis
mesh_terms: D002079:Butter / Q000032:analysis*; D002851:Chromatography, High Pressure Liquid / Q000295:instrumentation / Q000379:methods*; D007477:Ions; D000644:Quaternary Ammonium Compounds / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D013237:Stereoisomerism; D014280:Triglycerides / Q000032:analysis* / Q000737:chemistry*
chemical_list: D007477:Ions; D000644:Quaternary Ammonium Compounds; D014280:Triglycerides; D002079:Butter