The preparation of conjugated linoleic acid (CLA)-enriched free fatty acids by industrial processes compared with our biphasic isomerisation experiments in a special designed reactor enabling the preparation of CLA esters was evaluated. Our experiments further revealed the main disadvantage of semi-synthetic alkali isomerisation to be the formation of conjugated E,E-octadecadienoic acid isomers (2.92–3.44%) and the bioavailability of free fatty acid products. Urea fractionation technology improved the quality of the reaction mixture, but at the same time the yield of rumenic acid was decreased on purification. Therefore, we decided to apply complexes of noble metals in order to isomerise linoleic acid ester derivatives. The known Wilkinson’s hydrogenation catalyst, RhCl (PPh3)3, was found to be the most effective. We investigated the preparation of bioavailable CLA-enriched triacylglycerols. Special attention was paid to recycling of Wilkinson’s catalyst.
Akoh C.C., Lai O.-M. (2005): Healthful Lipids, Champaign, AOCS Press: 1–24.
Henry C.J.K. (2007): Novel Food Ingredients for Weight Control. 1st Ed. Woodhead Publishing Ltd.: 263–276.
AOCS (1997): Determination of cis- and trans- fatty acids in hydrogenated and refined oils and fats by capillary GLC, AOCS Official Method Ce 1f-96. Champaign, AOCS Press
Astruc D. (2007): Organometallic Chemistry and Catalysis. Berlin Heidelberg, Springer-Verlag: 367–392.
Bentley P. H., McCrae W. (1970): Synthesis of symmetrical 1,3-diglycerides. The Journal of Organic Chemistry, 35, 2082-2083 https://doi.org/10.1021/jo00831a105
Berdeaux O., Voinot L., Angioni E., Juanéda P., Sébédio J. L. (1998): A simple method of preparation of methyl trans-10,cis-12- and cis-9,trans-11-octadecadienoates from methyl linoleate. Journal of the American Oil Chemists' Society, 75, 1749-1755 https://doi.org/10.1007/s11746-998-0327-x
Biermann Ursula, Butte Werner, Eren Tarik, Haase Detlev, Metzger Jürgen O. (2007): Regio- and Stereoselective Diels–Alder Additions of Maleic Anhydride to Conjugated Triene Fatty Acid Methyl Esters. European Journal of Organic Chemistry, 2007, 3859-3862 https://doi.org/10.1002/ejoc.200700243
Christie W.W. (1989): Gas Chromatography and Lipids: A Practical Guide. The Oily Press Ltd.: 130–140.
Consorti Crestina S., Aydos Guilherme L.P., Ebeling Günter, Dupont Jaïrton (2009): Multiphase catalytic isomerisation of linoleic acid by transition metal complexes in ionic liquids. Applied Catalysis A: General, 371, 114-120 https://doi.org/10.1016/j.apcata.2009.09.042
Devillard Estelle, Andant Nicolas, John Wallace R. (2006): Increased expression of a molecular chaperone GroEL in response to unsaturated fatty acids by the biohydrogenating ruminal bacterium, Butyrivibrio fibrisolvens
. FEMS Microbiology Letters, 262, 244-248 https://doi.org/10.1111/j.1574-6968.2006.00399.x
Dobson Gary (1998): Identification of conjugated fatty acids by gas chromatography-mass spectrometry of 4-methyl-1,2,4-triazoline-3,5-dione adducts. Journal of the American Oil Chemists' Society, 75, 137-142 https://doi.org/10.1007/s11746-998-0024-9
Frankel E. N. (1970): Homogenous catalytic conjugation of polyunsaturated fats by chromium carbonyls. Journal of the American Oil Chemists Society, 47, 33-36 https://doi.org/10.1007/BF02541453
Ha Y.L., Grimm N.K., Pariza M.W. (1987): Anticarcinogens from fried ground beef: heat-altered derivatives of linoleic acid. Carcinogenesis, 8, 1881-1887 https://doi.org/10.1093/carcin/8.12.1881
Housecroft C.E., Sharpe A.G. (2014): Anorganická chemie (Czech translation of 4th Edition). Prague, VSCHT Praha: 917–945.
Hunter W.J., Baker F.C., Rosenfeld I.S., Keyser J.B., Tove S.B. (1976): Biohydrogenation of unsaturated fatty acids. Hydrogenation by cell-free preparations of Butyrivibrio fibrisolvens. Journal of Biological Chemistry, 251: 2241–2247.
IUPAC (1987): Determination of di- and tri-unsaturated fatty acids by ultraviolet spectrophotometry. Standard Methods for the Analysis of Oils, Fats and Derivatives, 5th Ed. Method 2.206. USA, IUPAC.
Jenkins T. C., Wallace R. J., Moate P. J., Mosley E. E. (2007): BOARD-INVITED REVIEW: Recent advances in biohydrogenation of unsaturated fatty acids within the rumen microbial ecosystem. Journal of Animal Science, 86, 397-412 https://doi.org/10.2527/jas.2007-0588
Kepler C.R., Tucker W.P., Tove S.B. (1971): Biohydrogenation of unsaturated fatty acids. V. Stereospecificity of proton addition and mechanism of action of linoleic acid Δ12-cis, Δ11-trans-isomerase from Butyrivibrio fibrisolvens. Journal of Biological Chemistry, 246: 2765–2771.
Köhler Peter, Grosch Werner (1999): Study of the Effect of DATEM. 1. Influence of Fatty Acid Chain Length on Rheology and Baking. Journal of Agricultural and Food Chemistry, 47, 1863-1869 https://doi.org/10.1021/jf980891i
Larock Richard C., Dong Xiaoyang, Chung Steven, Reddy Ch. Kishan, Ehlers Laurie E. (2001): Preparation of conjugated soybean oil and other natural oils and fatty acids by homogeneous transition metal catalysis. Journal of the American Oil Chemists' Society, 78, 447-453 https://doi.org/10.1007/s11746-001-0284-1
Liavonchanka Alena, Feussner Ivo (2008): Biochemistry of PUFA Double Bond Isomerases Producing Conjugated Linoleic Acid. ChemBioChem, 9, 1867-1872 https://doi.org/10.1002/cbic.200800141
Liavonchanka A., Hornung E., Feussner I., Rudolph M. G. (): Structure and mechanism of the Propionibacterium acnes polyunsaturated fatty acid isomerase. Proceedings of the National Academy of Sciences, 103, 2576-2581 https://doi.org/10.1073/pnas.0510144103
Leray C. (2015): Lipids: Nutrition and Health. CRC Press Taylor & Francis Group: 228–235.
Neises Bernhard, Steglich Wolfgang (1978): Simple Method for the Esterification of Carboxylic Acids. Angewandte Chemie International Edition in English, 17, 522-524 https://doi.org/10.1002/anie.197805221
Okuyama T., Maskill H. (2014): Organic Chemistry: A Mechanistic Approach. Oxford University Press: 127.
Pavia D.L., Lampman G.M., Kriz G.S., Vyvyan J.R. (2009): Introduction to Spectroscopy. 4th Ed. Brooks/Cole Cengage Learning: 445–492.
Singer H., Seibel R., Mees U. (1977): Die Isomerisierung des Linolsäuremethylesters mit Rhodiumkomplexen. Fette, Seifen, Anstrichmittel, 79, 147-150 https://doi.org/10.1002/lipi.19770790403
Velíšek J. (2002): Chemie potravin. Tábor, OSSIS: 81–87.
Villeneuve Pierre, Lago Regina, Barouh Nathalie, Barea Bruno, Piombo Georges, Dupré Jean-Yves, Guillou Anne, Pina Michel (2005): Production of conjugated linoleic acid isomers by dehydration and isomerization of castor bean oil. Journal of the American Oil Chemists' Society, 82, 261-269 https://doi.org/10.1007/s11746-005-1065-6
Yang Lin, Huang Yu, Wang Han Qing, Chen Zhen-Yu (2002): Production of conjugated linoleic acids through KOH-catalyzed dehydration of ricinoleic acid. Chemistry and Physics of Lipids, 119, 23-31 https://doi.org/10.1016/S0009-3084(02)00052-X
Young David C., Vouros Paul., Decosta Brian., Holick Michael F. (1987): Location of conjugated diene position in an aliphatic chain by mass spectrometry of the 4-phenyl-1,2,4-triazoline-3,5-dione adduct. Analytical Chemistry, 59, 1954-1957 https://doi.org/10.1021/ac00142a013