Monitoring cyclic acyloxonium ion formation in palmitin systems using infrared spectroscopy and isotope labelling technique

被引:28
作者
Rahn, Anja Katerina Karin [1 ]
Yaylayan, Varoujan Antranik [1 ]
机构
[1] McGill Univ, Dept Food Sci & Agr Chem, Quebec City, PQ H9X 3V9, Canada
基金
加拿大自然科学与工程研究理事会;
关键词
Acyloxonium ion; Dipalmitin; IR Spectroscopy; Isotope labelling; 3-monochloropropanediol (3-MCPD); Tripalmitin; FATTY-ACID ESTERS; CARBOHYDRATE CHEMISTRY; CARBOXONIUM COMPOUNDS; OILS; GLYCIDOL; SALTS;
D O I
10.1002/ejlt.201000426
中图分类号
TS2 [食品工业];
学科分类号
0832 ;
摘要
To confirm the possible involvement of acyloxonium ions as reactive intermediates in food related lipids, their formation was monitored in triplamitin, 1,2 dipalmitin, 1-monopalmitin and specifically labelled tripalmitin (1,1,1-(13)C(3)) using Fourier-transform IR spectroscopy (FTIR). Reactions were conducted at 100 degrees C using a mixture of ZnCl(2) and the lipids. When tripalmitin or 1,2-dipalmitin samples were heated at 100 degrees C in the presence of ZnCl(2) a new band centred at 1651 cm(-1) was formed and increased over time. When (13)C-labelled tripalmitin (1,1,1-(13)C(3)) was studied the spectrum exhibited an expected 40 cm(-1) shift from 1651 to 1611cm(-1) indicating the involvement of the carbonyl carbon in the formation of the band. The 1-monopalmitin generated a similar but weaker band at higher temperatures and requiring longer times. These observations may indicate that under hydrophobic environment acyloxonium ions are preferentially formed with neighbouring ester groups assisted by the catalytic action of a free hydroxyl group serving as a proton transfer site. In the absence of such a free hydroxyl group tripalmitin undergoes acyloxonium ion formation at a slower rate than 1,2-dipalmitoyl glycerol, whereas, 1-monopalmitoyl glycerol due to the absence of a neighbouring ester shows even slower transformation efficiencies. This order of reactivity may however change in the presence of water.
引用
收藏
页码:330 / 334
页数:5
相关论文
共 14 条
  • [1] MECHANISM OF FORMATION OF CHLOROPROPANOLS PRESENT IN PROTEIN HYDROLYSATES
    COLLIER, PD
    CROMIE, DDO
    DAVIES, AP
    [J]. JOURNAL OF THE AMERICAN OIL CHEMISTS SOCIETY, 1991, 68 (10) : 785 - 790
  • [2] Hamlet C.G., 2008, BIOACTIVE COMPOUNDS, P323
  • [3] Hamlet CG., 2009, PROCESS INDUCED FOOD, P175
  • [4] HART H, 1966, TETRAHEDRON LETT, V29, P3383
  • [5] MODES OF REACTION OF AMBIDENT CATIONS
    HUNIG, S
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1964, 3 (08) : 548 - +
  • [6] A New Analytical Method for the Quantification of Glycidol Fatty Acid Esters in Edible Oils
    Masukawa, Yoshinori
    Shiro, Hiroki
    Nakamura, Shun
    Kondo, Naoki
    Jin, Norikazu
    Suzuki, Nobuyoshi
    Ooi, Naoki
    Kudo, Naoto
    [J]. JOURNAL OF OLEO SCIENCE, 2010, 59 (02) : 81 - 88
  • [7] CARBOXONIUM COMPOUNDS IN CARBOHYDRATE CHEMISTRY .25. SYNTHESIS OF ACYLOXONIUM IONS BY REACTION OF TRIFLUOROMETHANESULFONIC ACID WITH DIOLESTERS AND TRIOLESTERS
    PAULSEN, H
    MEYBORG, H
    [J]. CHEMISCHE BERICHTE-RECUEIL, 1975, 108 (10): : 3176 - 3189
  • [8] CARBOXONIUM COMPOUNDS IN CARBOHYDRATE CHEMISTRY .13. SYNTHESIS AND VALENCE ISOMERISM OF ACYLOXONIUM SALTS OF 1.2.3-TRIOLS
    PAULSEN, H
    BEHRE, H
    [J]. CHEMISCHE BERICHTE-RECUEIL, 1971, 104 (04): : 1281 - &
  • [9] CARBOXONIUM COMPOUNDS IN CARBOHYDRATE CHEMISTRY .12. SYNTHESIS OF ACYLOXONIUM SALTS OF 1.2-DIOLS AND 1.3-DIOLS
    PAULSEN, H
    BEHRE, H
    [J]. CHEMISCHE BERICHTE-RECUEIL, 1971, 104 (04): : 1264 - &
  • [10] PAULSON H, 1971, ADV CARBOHYD CHEM, P127