메뉴 건너뛰기




Volumn 126, Issue 4, 2004, Pages 1063-1072

Regioselective Cis-Trans Isomerization of Arachidonic Double Bonds by Thiyl Radicals: The Influence of Phospholipid Supramolecular Organization

Author keywords

[No Author keywords available]

Indexed keywords

BIOMARKERS; CHEMICAL BONDS; FREE RADICALS; ISOMERIZATION; PHOSPHOLIPIDS; STEREOCHEMISTRY; SUPRAMOLECULAR CHEMISTRY;

EID: 0942287124     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja038072o     Document Type: Article
Times cited : (109)

References (96)
  • 5
    • 0003456468 scopus 로고
    • Ando, W., Ed.; Wiley: New York
    • (a) Niki, E. In Organic Peroxides; Ando, W., Ed.; Wiley: New York, 1992; pp 764-787.
    • (1992) Organic Peroxides , pp. 764-787
    • Niki, E.1
  • 6
    • 0003157159 scopus 로고
    • Yu, B. P., Ed.; CRC Press: Boca Raton, FL
    • (b) Yu, B. P. In Free Radicals in Aging; Yu, B. P., Ed.; CRC Press: Boca Raton, FL 1993; pp 57-88.
    • (1993) Free Radicals in Aging , pp. 57-88
    • Yu, B.P.1
  • 18
    • 0034679015 scopus 로고    scopus 로고
    • The cis-trans isomerization of monounsaturated fatty acid methyl esters and residues in phospholipids has been studied in some details, including a kinetic study of individual reactions and the influence of antioxidant vitamins. See: (a) Chatgilialoglu, C.; Ferreri, C.; Ballestri, M.; Mulazzani, Q. G.; Landi, L. J. Am. Chem. Soc. 2000, 122, 4593-4601.
    • (2000) J. Am. Chem. Soc. , vol.122 , pp. 4593-4601
    • Chatgilialoglu, C.1    Ferreri, C.2    Ballestri, M.3    Mulazzani, Q.G.4    Landi, L.5
  • 26
    • 0004144598 scopus 로고    scopus 로고
    • Sébédio J. L., Christie, W. W., Eds.; The Oily Press: Dundee, U.K.
    • Trans Fatty Acids in Human Nutrition; Sébédio J. L., Christie, W. W., Eds.; The Oily Press: Dundee, U.K., 1998.
    • (1998) Trans Fatty Acids in Human Nutrition
  • 32
    • 0942306234 scopus 로고    scopus 로고
    • The estimation of trans fatty acids in foods is one of the 2003 priorities listed by the Food and Drug Administration of the U.S.A. (see: http://www.cfsan.fda.gov/~dms/cfsan303.html).
  • 34
    • 0942295591 scopus 로고    scopus 로고
    • Allison, A. Nature 2002, 420, 600-601.
    • (2002) Nature , vol.420 , pp. 600-601
    • Allison, A.1
  • 36
    • 0035976575 scopus 로고    scopus 로고
    • Funk, C. D. Science 2001, 294, 1871-1875.
    • (2001) Science , vol.294 , pp. 1871-1875
    • Funk, C.D.1
  • 46
    • 0942284609 scopus 로고    scopus 로고
    • note
    • When trans isomers of linoleic acid derived from altered fats are ingested and metabolized,32-36 arachidonate moieties found in tissues contain the 11 and 14 double bonds in the trans configuration.
  • 53
    • 0001578877 scopus 로고    scopus 로고
    • Supramolecular systems can reduce selectivity in chemical processes. For examples, see: (a) Blatter, F.; Sun, H.; Vasenkov, S.; Frei, H. Catal. Today 1998, 41, 297-309.
    • (1998) Catal. Today , vol.41 , pp. 297-309
    • Blatter, F.1    Sun, H.2    Vasenkov, S.3    Frei, H.4
  • 60
    • 0942306231 scopus 로고    scopus 로고
    • note
    • Rate constants are measured in water.41 Since the rates of thiol trapping of alkyl radicals are solvent-dependent.42 it is expected that these values be slightly slower in i-PrOH.
  • 63
    • 0010253461 scopus 로고
    • Patai, S., Ed.; Wiley: London
    • Knight, A. R. In The Chemistry of Thiol Group; Patai, S., Ed.; Wiley: London, 1974; Part 1, pp 455-479.
    • (1974) The Chemistry of Thiol Group , Issue.PART 1 , pp. 455-479
    • Knight, A.R.1
  • 68
    • 0942273791 scopus 로고    scopus 로고
    • note
    • -8 M.11c
  • 69
    • 0942273790 scopus 로고    scopus 로고
    • note
    • In our previous article on the isomerization of methyl arachidonate carried out by γ-irradiation, we used equimolar quantities (150 mM) of methyl ester and 2-mercaptoethanol. Under these conditions, after 5 kGy irradiation the all-cis isomer was halved, whereas the overall geometrical isomer yield was found to be ca. 75%. A fraction of ca. 20% yield was characterized as a mixture of thiol-methyl arachidonate adducts. To avoid the adduct formation, in this work we dropped the fatty acid contents of PC to 15 mM (10 times lower), which in terms of double bond molarity means a decrease of ca. 50 times. Furthermore, we decreased the concentration of thiol from 150 mM to 7 mM, i.e., ca. 20 times.
  • 71
    • 0942306232 scopus 로고    scopus 로고
    • note
    • Under these conditions, the saturated fatty acids (stearate moieties) are not evidenced. Stearic acid moieties could be detected by heating the plate sprayed with a 40% sulphuric acid aqueous solution.
  • 76
    • 0002916557 scopus 로고    scopus 로고
    • Alfassi, Z. B., Ed.; Wiley: Chichester, U.K.
    • Wardman, P. In S-Centered Radicals; Alfassi, Z. B., Ed.; Wiley: Chichester, U.K., 1999; pp 289-309.
    • (1999) S-Centered Radicals , pp. 289-309
    • Wardman, P.1
  • 77
    • 0942306230 scopus 로고    scopus 로고
    • note
    • A mechanistic study that settles differences between the product studies and the pulse radiolysis results as well as the competition kinetics between isomerization and peroxidation processes is beyond the scope of this paper. Work is in progress to address properly the reaction mechanism.
  • 79
    • 0004273681 scopus 로고
    • New, R. R. C., Ed.: IRL Press: Oxford, U.K.
    • Liposomes: A Practical Approach; New, R. R. C., Ed.: IRL Press: Oxford, U.K., 1990.
    • (1990) Liposomes: A Practical Approach
  • 81
    • 0942306233 scopus 로고    scopus 로고
    • note
    • No isomerization was detected upon UV- or γ-irradiating samples without thiol.
  • 82
    • 0942273792 scopus 로고    scopus 로고
    • note
    • 13C NMR for the identification of cis/trans isomers is well-documented.60,61 Early work on the spectra of arachidonic acid methyl ester60 and its mono-5-trans24 and mono-14-trans isomers25 evidenced that the ethylenic carbon atom resonance in position 15 is indeed meaningful for these isomers.
  • 86
    • 0942273793 scopus 로고    scopus 로고
    • note
    • Evidence that cis-trans isomerization of unsaturated fatty acids can occur endogenously both in membrane phospholipids and fat depots has recently been gathered. Indeed, rats fed a diet completely deprived of trans fatty acids showed trans isomers of 18:1, 18:2, and 20:4 in different percentages depending on the kinds of tissue extracts (manuscript in preparation).
  • 93
    • 0035986472 scopus 로고    scopus 로고
    • and reference cited therein
    • Wolff, R. L.; Precht, D. Lipids 2002, 37, 627-629 and reference cited therein.
    • (2002) Lipids , vol.37 , pp. 627-629
    • Wolff, R.L.1    Precht, D.2
  • 94
    • 0942284608 scopus 로고    scopus 로고
    • Reference 39, p 100
    • Reference 39, p 100.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.