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Diagram showing glycerol (1) and all the possible acetate esters of glycerol (2-6)

In organic chemistry glycerolysis refers to any process in which chemical bonds are broken via a reaction with glycerol. The term refers almost exclusively to the transesterification reaction of glycerol with triglycerides (fats/oils) to form mixtures of monoglycerides and diglycerides. These find a variety of uses; as food emulsifiers (e.g. E471), 'low fat' cooking oils (e.g. diacylglycerol oil) and surfactants (such as monolaurin).

The transesterification process gives a complex mixture of products, however not all of these are of equivalent use.[1] This has led to the development of optimized processes able to produce better defined products; in particular by using enzymes,[2] reactions in supercritical carbon dioxide and flow chemistry.[3] The production of diglycerides (often called diacylglycerols or DAGs) has been investigated extensively due to their use in foods, with total annual sales of approximately US$200 million in Japan since its introduction in the late 1990s until 2009.[2][4]

Enzymatic glycerolysis of vegetable fats and oils

Partial acylglycerols, mono- and diacylglycerols (MAGs and DAGs), are industrially produced on the basis of a batch alkaline-catalyzed chemical glycerolysis of edible natural fats and oils at high temperatures (220-250℃) and elevated pressure under nitrogen atmosphere. The process consumes high energy, and the row products have poor quality, i.e. low yield (<50%), dark-colored and burned-tasting due to high reaction temperature, which requires extensive and costly purification steps. The chemical glycerolysis of fat and oil was reviewed in 1982(Refer to the Reference [1]).
Contrary to the chemical process, enzyme (usually lipase)-catalyzed glycerolysis of fat and oil is carried out at much lower temperature (5-65℃) under atmospheric air pressure resulting in no dark-color and no burned taste, but requires much longer reaction time (2-3 days).
The first scientific article concerning lipase-catalyzed glycerolysis of fats and oils was published in 1986,[5] followed by several articles by the same group.[6][7][8][9][10][11] Later up to recently a number of papers have been published concerning lipase (free or immobilized)-catalyzed glycerolysis of fat and oils[12][13][14][15][16][17][18][19][20][21].
Most researchers have been tried to produce MAGs or DAGs from vegetable oils through biochemical approach (i.e. lipase catalyzed glycerolysis), however, it was suggested that the products themselves after just separation of the immobilized enzyme particles by centrifuge without subsequent purification (mixture of MAGs, DAGs and remaining unreacted TAGs without the addition of saturated or hydrogenated fat, thus not altering fatty acid compositions), which do not contain any trans fatty acid nor cholesterol, could be utilized as a kind of margarine (named glycerolysis structured oils).[22][23][24]

See also

References

  1. ^ Sonntag, Norman O. V. (1982). "Glycerolysis of fats and methyl esters — Status, review and critique". Journal of the American Oil Chemists' Society. 59 (10): 795A – 802A. doi:10.1007/BF02634442. ISSN 0003-021X.
  2. ^ a b Phuah, Eng-Tong; Tang, Teck-Kim; Lee, Yee-Ying; Choong, Thomas Shean-Yaw; Tan, Chin-Ping; Lai, Oi-Ming (2015). "Review on the Current State of Diacylglycerol Production Using Enzymatic Approach" (PDF). Food and Bioprocess Technology. 8 (6): 1169–1186. doi:10.1007/s11947-015-1505-0. ISSN 1935-5130.
  3. ^ Junior, Ivaldo I.; Flores, Marcela C.; Sutili, Felipe K.; Leite, Selma G. F.; de M. Miranda, Leandro S.; Leal, Ivana C. R.; de Souza, Rodrigo O. M. A. (2012). "Lipase-Catalyzed Monostearin Synthesis under Continuous Flow Conditions". Organic Process Research & Development. 16 (5): 1098–1101. doi:10.1021/op200132y. ISSN 1083-6160.
  4. ^ Lo, Seong-Koon; Tan, Chin-Ping; Long, Kamariah; Yusoff, Mohd. Suria Affandi; Lai, Oi-Ming (2008). "Diacylglycerol Oil—Properties, Processes and Products: A Review" (PDF). Food and Bioprocess Technology. 1 (3): 223–233. doi:10.1007/s11947-007-0049-3. ISSN 1935-5130.
  5. ^ Tsuneo Yamane, Mohammad Mozammel Hoq, Sumiyo Itoh and Shoichi Shimizu (1986). “Glycerolysis of fat by lipase”. Journal of the Japan Oil Chemists' Society, 35(8): 625-631.
  6. ^ Gerald P. McNeill, Shoichi Shimizu and Tsuneo Yamane (1990).“Solid phase enzymatic glycerolysis of beef tallow resulting in a high yield of monoglycerides”. Journal of the American Oil Chemists' Society, 67(11): 779-783.
  7. ^ Gerald P. McNeill, Shoichi Shimizu and Tsuneo Yamane (1991). “High yield enzymatic glycerolysis of fats and oils”. Journal of the American Oil Chemists' Society, 68(1): 1-5.
  8. ^ Gerald P. McNeill and Tsuneo Yamane (1991). “Further improvements in the yield of monoglycerides during enzymatic glycerolysis of fats and oils”. Journal of the American Oil Chemists' Society, 68(1): 6-10.
  9. ^ Tsuneo Yamane, Sung The Kang, Katsuyoshi Kawahara and Yoshito Koizumi (1994). “High-yield diacylglycerol formation by solid-phase enzymatic glycerolysis of hydrogenated beef tallow”. Journal of the American Oil Chemists' Society, 71(3): 339-342.
  10. ^ Uwe T. Bornscheuer and Tsuneo Yamane (1994) “Activity and stability of lipase in the solid-phase glycerolysis of triolein”. Enzyme and Microbial Technology, 16(10): 864-869.
  11. ^ Roxana Rosu, Yuki Uozaki, Yugo Iwasaki and Tsuneo Yamane (1997). “Repeated use of immobilized lipase for monoacylglycerol production by solid phase glycerolysis of olive oil”. Journal of the American Oil Chemists’ Society, 74(4): 445-450.
  12. ^ H. Noureddini, S.E. Harmeier (1998). “Enzymatic glycerolysis of soybean oil"Journal of the American Oil Chemists’ Society, 75: 1359-1365.
  13. ^ Elfman-Borjesson, M. Harrod (1999). “Synthesis of monoglycerides by glycerolysis of rapeseed oil using immobilized lipase” Journal of the American Oil Chemists’ Society, 76: 701-707.
  14. ^ M. Tüter, H.A. Aksoy (2005). “Enzymatic glycerolysis of palm and palm kernel oils”Chemical Engineering Communications, 192: 14-17.
  15. ^ T. Yang, M. Rebsdorf, U. Engelrud, X. Xu (2005). “Enzymatic production of monoacylglycerols containing polyunsaturated fatty acids through an efficient glycerolysis approach” Journal of Agricultural Food Chemistry, 53:1475-1481.
  16. ^ P.B.L. Fregolente, L.V. Fregolente, G.M.F. Pinto, B.C. Batistella, M.R. Wolf-Maciel, R.M. Filho (2008). “Monoglycerides and diglycerides synthesis in a solvent-free system by lipase-catalyzed glycerolysis” Applied Biochemistry and Biotechnology, 146: 165-172.
  17. ^ Lo, Seong-Koon; Tan, Chin-Ping; Long, Kamariah; Yusoff, Mohd. Suria Affandi; Lai, Oi-Ming (2008). "Diacylglycerol Oil—Properties, Processes and Products: A Review" (PDF). Food and Bioprocess Technology. 1(3): 223–233. doi:10.1007/s11947-007-0049-3. ISSN 1935-5130.
  18. ^ M.K. Naik, S.N. Naik, S. Mohanty (2014). “Enzymatic glycerolysis for conversion of sunflower oil to food based emulsifiers” Catalysis Today, 237: 145-149.
  19. ^ Phuah, Eng-Tong; Tang, Teck-Kim; Lee, Yee-Ying; Choong, Thomas Shean-Yaw; Tan, Chin-Ping; Lai, Oi-Ming (2015). "Review on the Current State of Diacylglycerol Production Using Enzymatic Approach" (PDF). Food and Bioprocess Technology. 8 (6): 1169–1186. doi:10.1007/s11947-015-1505-0. ISSN 1935-5130.
  20. ^ T.S.Y. Choong, C.M. Yeoh, E.T. Phuah, W.L. Siew, Y.Y. Lee, T.K. Tang, L.C. Abdullah (2018). “Kinetic study of lipase-catalyzed glycerolysis of palm olein using Lipozym TLIM in solvent-free system” PLoS One, 13, Article e0192375.
  21. ^ Shangde Sun, Yaping Lv, Gaoshang Wang (2020). “Enhanced surfactant production using glycerol-based deep eutectic solvent as a novel reaction medium for enzymatic glycerolysis of soybean oil” Industrial Crops and Products, 151, Article 112470.
  22. ^ R.A. Nicholson, A.G. Marangoni (2020). “Enzymatic glycerolysis converts vegetable oils into structural fats with the potential to replace palm oil in food products” Nature Food, 1: 684-692.
  23. ^ R.A. Nicholson, A.G. Marangoni (2021). “Lipase-catalyzed glycerolysis extended to the conversion of a variety of edible oils into structural fats” Current Research in Food Science, 4: 163-174.
  24. ^ Reed A Nicholson and Alejandro G Marangoni (2022). “Glycerolysis structured oils as natural fat replacement“ Current Opinion in Food Science, 43: 1-6.

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