Quantification of eicosapentaenoic and docosahexaenoic acid geometrical isomers formed during fish oil deodorization by gas-liquid chromatography.
ABSTRACT Long-chain polyunsaturated fatty acids (LC-PUFAs) of the n-3 series and especially eicosapentaenoic and docosahexaenoic acids (EPA and DHA, respectively) have important biological properties. The main dietary sources of LC-PUFAs are fish and fish oil. Geometrical isomerization is one of the main reactions happening during the thermal treatment of polyunsaturated fatty acids. Refined fish oils are used to supplement food products in LC-PUFAs and the quality of these nutritional ingredients have to be controlled. In the present study, a suitable method for the quantification of EPA and DHA geometrical isomers in fish oils by gas-liquid chromatography (GC) is presented. A highly polar capillary column (CP-Sil 88, 100 m) operating under optimal conditions was used. Method selectivity was studied by GC-mass spectrometry. The performance characteristics of the quantification method were studied using samples of fish oil deodorized at 220 degrees C for 3 h. The linearity of the method was assessed by analyzing composite samples obtained by mixing fish oil deodorized at 220 degrees C with semi-refined fish oil (control). Precision was evaluated by analyzing the same samples in triplicate. Results showed that the validated method is suitable to quantify low amounts of geometrical (trans) isomers of EPA and DHA in refined fish oils. The limits of quantification of the EPA and DHA geometrical isomers are 0.16 and 0.56 g/100 g of fish oil, for EPA and DHA, respectively. Commercially available LC-PUFA oil samples were evaluated by using the validated method. The results show that the oils analyzed contain low amounts (<1% of total fatty acids) of geometrical isomers of EPA and DHA.
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ABSTRACT: Commercial fish oils and foods containing fish may contain trans and/or isomerized fatty acids (FA) produced during processing or as part of prepared foods. The current American Oil Chemists' Society (AOCS) official method for marine oils (method Ce 1i-07) is based on separation by use of poly(ethylene glycol) (PEG) columns, for example Supelcowax-10 or equivalent, which do not resolve most unsaturated FA geometric isomers. Highly polar 100-m cyanopropyl siloxane (CPS) columns, for example SP-2560 and CP Sil 88 are recommended for separation of geometric FA isomers. Complementary separations were achieved by use of two different elution temperature programs with the same CPS column. This study is the first direct comparison of the separations achieved by use of 30-m Supelcowax-10 and 100-m SP-2560 columns for fatty acid methyl esters (FAME) prepared from the same fish oil and fish muscle sample. To simplify the identification of the FA in these fish samples, FA were fractionated on the basis of the number and type of double bonds by silver-ion solid-phase extraction (Ag⁺-SPE) before GC analysis. The results showed that a combination of the three GC separations was necessary to resolve and identify most of the unsaturated FA, FA isomers, and other components of fish products, for example phytanic and phytenic acids. Equivalent chain length (ECL) values of most FAME in fish were calculated from the separations achieved by use of both GC columns; the values obtained were shown to be consistent with previously reported values for the Supelcowax-10 column. ECL values were also calculated for the FA separated on the SP-2560 column. The calculated ECL values were equally valid under isothermal and temperature-programmed elution GC conditions, and were valuable for confirmation of the identity of several unsaturated FAME in the fish samples. When analyzing commercially prepared fish foods, deodorized marine oils, or foods fortified with marine oils it is strongly recommended that quantitative data acquired by use of PEG columns is complemented with data obtained from separations using highly polar CPS columns.Lipids 03/2012; 47(3):329-44. · 2.56 Impact Factor
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ABSTRACT: The levels of trans isomers of eicosapentaenoic (EPA) acid and docosahexaenoic acid (DHA) in 77 omega-3 products on the European market have been studied. Fatty acids were analyzed as fatty acid methyl esters by gas chromatography with a flame ionization detector, using a cyanopropyl coated stationary phase. The amount of mono-trans EPA isomers relative to the corresponding all-cis isomer ranged from 0.19 to 4.5 %. The corresponding values for mono-trans DHA relative to the all-cis isomer ranged from 0.25 to 5.9 %. There was a strong correlation between the degree of isomerization of EPA and DHA, showing that DHA was 1.26 times more isomerized than EPA. Division of the samples into different product groups showed that samples with a low degree of isomerization were found in all groups, except one. This shows that a high degree of isomerization is avoidable, and also points to deodorization of the oils as the main source of trans isomers.Lipids 05/2012; 47(7):659-67. · 2.56 Impact Factor
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ABSTRACT: Fish oils have many dietary benefits, but have strong odours and are easily oxidised. For these reasons, β-cyclodextrin (β-CD) a water-soluble polymer and polycaprolactone (PCL) a water-insoluble polymer were used to encapsulate fish oil in this study. In addition, the stabilities of freeze-dried fish oil (FO) in encapsulated complexes were investigated to determine fish oil release rates at different relative humidities and storage temperatures. In order to facilitate the practical applications of the water-soluble and insoluble fish oil complexes produced, release studies of fish oil were performed in de-ionised water, NaCl solution and fish sauce. Based on our studies, fish oil loaded β-CD at a mixing ratio of 10:20 (β-CD:FO (w:w)) was the best composition in terms of encapsulation efficiency (84.1%), fish oil loading (62.7%), fish oil leakage after freeze-drying (11.0%), and eicopentaenoic acid (EPA) encapsulation efficiency (6.5%). In addition, fish oil release rates from β-CD particles were slower in de-ionised water and in 15% and 25% NaCl than in fish sauce at all mixing ratios between β-CD and FO. The storage stabilities of freeze-dried β-CD–FO complexes at 10:20 (w:w) mixing ratio at various relative humidities retained 97% of fish oil within the particles during 3 days. However, the release rate of fish oil from β-CD–FO complexes of 10:20 mixing ratio was accelerated in fish sauce. In terms of the emulsion–diffusion method, PCL more efficiently retarded the release of FO in liquid or powder form, although particles were broken by freeze-drying. It is supposed that PCL better protected FO because of its water insolubility.Food Chemistry 01/2010; 119(4):1694-1703. · 3.33 Impact Factor