1H-NMR Characterization of Epoxides Derived from Polyunsaturated Fatty Acids

详细信息    查看全文

• 作者：Wei Xia ; Suzanne M. Budge ; Mike D. Lumsden
• 关键词：1H NMR ; Lipid oxidation ; Canola oil ; Fish oil ; Stereoisomer ; Diepoxide ; Triepoxide
• 刊名：Journal of the American Oil Chemists' Society
• 出版年：2016
• 出版时间：April 2016
• 年：2016
• 卷：93
• 期：4
• 页码：467-478
• 全文大小：676 KB
• 参考文献：1.Sharma BK, Adhvaryu A, Liu Z, Erhan SZ (2006) Chemical modification of vegetable oils for lubricant applications. J Am Oil Chem Soc 83:129–136CrossRef
  2.Mungroo R, Pradhan NC, Goud VV, Dalai AK (2008) Epoxidation of canola oil with hydrogen peroxide catalyzed by acidic ion exchange resin. J Am Oil Chem Soc 85:887–896CrossRef
  3.Schaich KM (2012) Thinking outside the classical chain reaction box of lipid oxidation. Lipid Technol 24:55–58CrossRef
  4.Yin H, Xu L, Porter NA (2011) Free radical lipid peroxidation: mechanisms and analysis. Chem Rev 111:5944–5972CrossRef
  5.Frankel EN (1984) Chemistry of free radical and singlet oxidation of lipids. Prog Lipid Res 23:197–221CrossRef
  6.Firestone D (2009) Official methods and recommended practices of the AOCS, Method Cd 9-57, 6th edn. AOCS Press, Champaign
  7.Hammock LG, Hammock BD, Casida JE (1974) Detection and analysis of epoxides with 4-(p-nitrobenzyl)-pyridine. Bull Environ Contam Toxicol 12:759–764CrossRef
  8.Dupard-Julien CL, Kandlakunta B, Uppu RM (2007) Determination of epoxides by high-performance liquid chromatography following derivatization with N,N-diethyldithiocarbamate. Anal Bioanal Chem 387:1027–1032CrossRef
  9.Mubiru E, Shrestha K, Papastergiadis A, De Meulenaer B (2014) Development and validation of a gas chromatography-flame ionization detection method for the determination of epoxy fatty acids in food matrices. J Agric Food Chem 62:2982–2988CrossRef
  10.Goicoechea E, Guillen MD (2010) Analysis of hydroperoxides, aldehydes and epoxides by 1H nuclear magnetic resonance in sunflower oil oxidized at 70 and 100 degrees C. J Agric Food Chem 58:6234–6245CrossRef
  11.Hwang HS, Erhan SZ (2006) Synthetic lubricant basestocks from epoxidized soybean oil and Guerbet alcohols. Ind Crops Prod 23:311–317CrossRef
  12.Aerts HAJ, Jacobs PA (2004) Epoxide yield determination of oils and fatty acid methyl esters using 1H NMR. J Am Oil Chem Soc 81:841–846CrossRef
  13.Lathi P, Mattiasson B (2007) Green approach for the preparation of biodegradable lubricant base stock from epoxidized vegetable oil. Appl Catal B 69:207–212CrossRef
  14.Sammaiah A, Padmaja KV, Prasad RB (2014) Synthesis of epoxy jatropha oil and its evaluation for lubricant properties. J Oleo Sci 63:637–643CrossRef
  15.Martínez-Yusta A, Goicoechea E, Guillén MD (2014) A review of thermo-oxidative degradation of food lipids studied by 1H NMR spectroscopy: influence of degradative conditions and food lipid nature. Compr Rev Food Sci Food Saf 13:838–859CrossRef
  16.Campanella A, Rustoy E, Baldessari A, Baltanas MA (2010) Lubricants from chemically modified vegetable oils. Bioresour Technol 101:245–254CrossRef
  17.Global Organization for EPA and DHA omega-3. GOED Voluntary Monograph. http://​www.​goedomega3.​com/​index.​php/​files/​download/​155 . Accessed Sept 2014
  18.Sullivan JC, Budge SM, St-Onge M (2010) Modeling the primary oxidation in commercial fish oil preparations. Lipids 46:87–93CrossRef
  19.Anuar ST, Zhao YY, Mugo SM, Curtis J (2012) Monitoring the epoxidation of canola oil by non-aqueous reversed phase liquid chromatography/mass spectrometry for process optimization and control. J Am Oil Chem Soc 89:1951–1960CrossRef
  20.Mudhaffar B, Salimon J (2010) Epoxidation of vegetable oils and fatty acids: catalysts, methods and advantages. J Appl Sci 10:1545–1553CrossRef
  21.Dinda S, Patwardhan AV, Goud VV, Pradhan N (2008) Epoxidation of cottonseed oil by aqueous hydrogen peroxide catalysed by liquid inorganic acids. Bioresour Technol 99:3737–3744CrossRef
  22.Marmesat S, Velasco J, Dobarganes MC (2008) Quantitative determination of epoxy acids, keto acids and hydroxy acids formed in fats and oils at frying temperatures. J Chromatogr A 1211:129–134CrossRef
  23.Guillén MD, Ruiz A (2004) Study of the oxidative stability of salted and unsalted salmon fillets by 1H nuclear magnetic resonance. Food Chem 86:297–304CrossRef
  24.Choe E, Min DB (2007) Chemistry of deep-fat frying oils. J Food Sci 72:77–86CrossRef
  25.Miyake Y, Yokomizo K, Matsuzaki N (1998) Determination of unsaturated fatty acid composition by high-resolution nuclear magnetic resonance spectroscopy. J Am Oil Chem Soc 75:1091–1094CrossRef
  26.Fankhauser-Noti A, Fiselier K, Biedermann-Brem S, Grob K (2006) Assessment of epoxidized soy bean oil (ESBO) migrating into foods: Comparison with ESBO-like epoxy fatty acids in our normal diet. Food Chem Toxicol 44:1279–1286CrossRef
  27.Piazza GJ, Nuñez A, Foglia TA (2003) Epoxidation of fatty acids, fatty methyl esters, and alkenes by immobilized oat seed peroxygenase. J Mol Catal B Enzym 21:143–151CrossRef
  28.Biedermann-Brem S, Biedermann M, Fankhauser-Noti A, Grob K, Helling R (2007) Determination of epoxidized soy bean oil (ESBO) in oily foods by GC–FID or GC–MS analysis of the methyl diepoxy linoleate. Eur Food Res Technol 224:309–314CrossRef
  29.Clayden J, Greeves N, Warren SG (2012) Organic chemistry, 2nd edn. Oxford University Press, Oxford/New York
  30.Bach RD, Canepa C, Winter JE, Blanchette PE (1997) Mechanism of acid-catalyzed epoxidation of alkenes with peroxy acids. J Org Chem 62:5191–5197CrossRef
  31.Falch E, Anthonsen HW, Axelson DE, Aursand M (2004) Correlation between 1H NMR and traditional methods for determining lipid oxidation of ethyl docosahexaenoate. J Am Oil Chem Soc 81:1105–1110CrossRef
  32.Marks DW, Larock RC (2002) The conjugation and epoxidation of fish oil. J Am Oil Chem Soc 79:65–68CrossRef
  33.Okovytyy SI, Kasyan LI, Seferova MF, Rossikhin VV, Svjatenko LK, Leszczynski J (2005) Identification of the stereoisomers of tetrahydroindene diepoxide by the 1H and 13C NMR characteristics: a combined experimental and theoretical study. J Mol Struct THEOCHEM 730:125–132CrossRef
  34.Maerker G, Haeberer ET, Herb SF (1966) Epoxidation of methyl linoleate. II. The two isomers of methyl 9,10:12,13-diepoxystearate. J Am Oil Chem Soc 43:505–508CrossRef
  35.Emken EA (1971) Determination of cis and trans in monoene and diene fatty esters by gas chromatography. Lipids 6:686–687CrossRef
  36.Lambert JB, Shurvell HF, Lightner DA, Cooks RG (1987) Introduction to organic spectroscopy (Chapter 3). Macmillan Publishing Company, New York
  37.Marks DW, Li F, Pacha CM, Larock RC (2001) Synthesis of thermoset plastics by Lewis acid initiated copolymerization of fish oil ethyl esters and alkenes. J Appl Polym Sci 81:2001–2012CrossRef
  38.Gunstone FD, Harwood JL, Dijkstra AJ (2007) The lipid handbook with CD-ROM, 3rd edn. CRC Press, Boca Raton
  39.Schaich KM (2005) Lipid oxidation: theoretical aspects. In: Shahidi F (ed) Bailey’s industrial oil and fat products. Wiley, Hoboken
  
• 作者单位：Wei Xia (1)
  Suzanne M. Budge (1)
  Mike D. Lumsden (2)
  
  1. Department of Process Engineering and Applied Science, Dalhousie University, 1360 Barrington St., Halifax, NS, B3J 1Z1, Canada
  2. Department of Chemistry, Dalhousie University, Halifax, NS, B3H 4J3, Canada
  
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Industrial Chemistry and Chemical Engineering
  Analytical Chemistry
  Chemistry
  Biotechnology
  Biomaterials
  Agriculture
  
• 出版者：Springer Berlin / Heidelberg
• ISSN：1558-9331

文摘

In recent years, 1H NMR has been used to study epoxides in lipid oxidation and industrial processes, but the peak assignments reported for monoepoxides and diepoxides have been inconsistent. Lack of clear assignments for chemical shifts of epoxides derived from polyunsaturated fatty acids (PUFA) has also limited the use of 1H NMR in detecting and quantifying these products during both oxidative degradation and industrial epoxidation. In this study, 1H NMR was used to characterize the epoxides synthesized from trilinolein, trilinolenin, canola oil, and fish oils by reaction with formic acid and hydrogen peroxide. Assignments for epoxides derived from PUFA in canola oil and fish oil were between 2.90–3.23 ppm and 2.90–3.28 ppm, distinct from other chemical groups in these oils. Chemical shifts of epoxy groups moved downfield with an increasing number of epoxy groups in the fatty acid chain. Hence, peaks for diepoxides appeared at 3.00, 3.09, and 3.14 ppm and for triepoxides at 3.00, 3.16, and 3.21 ppm. Results also suggested that stereoisomers of diepoxides and triepoxides were formed during the epoxidation process under the conditions of this study. These new assignments for di- and tri-epoxide stereoisomers were supported by GC–MS analysis of their methyl esters, H–H COSY experiments, and a re-evaluation of several previous epoxide-related studies.