Rapid quantitation of fish oil fatty acids and their ethyl esters by FT‐NIR models

Consumption of fish oil and dietary supplements containing eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) has steadily increased because of their reported health benefits. A rapid procedure based on Fourier Transform Near Infrared Spectroscopy (FT‐NIR) models was developed for analysis of fish oil and their ethyl ester derivatives to replace the time consuming GC method. Inclusion of fish oil or ethyl esters containing varied concentrations of OA, EPA, and DHA into the FT‐NIR classification models made possible their classification and quantification. Accurate GC analysis is essential in developing reliable quantitative models since FT‐NIR is matrix dependent. Development of FT‐NIR models based on 30 m PEG capillary GC column results, as recommended by the official GC method for analysis of marine oils, proved problematic, since these columns did not resolve many geometric isomers compared to 100 m highly polar cyanopropyl polysiloxane columns. Depending on the content of geometric isomers in fish oils and ethyl esters, the levels of long‐chain n‐3 PUFA would be overestimated if the model used were based on the results from a 30 m column. The FT‐NIR method was found to be applicable to all fish oil and ethyl ester samples, except when fatty acids were outside the range examined, or contaminants were present. The FT‐NIR method was applicable to analysis of in‐plant intermediates provided contaminants were absent, or identified so they could be incorporated into the model. The FT‐NIR method was suitable to evaluate the shelf life of n‐3 PUFA concentrates.     

Determination of fatty acids and some undesirable fatty acid isomers in selected Turkish margarines

The fatty acid composition and total trans fatty acid content in 10 margarines produced in Turkey were determined by capillary gas chromatography and Fourier transform‐infrared spectroscopy (FT‐IR) spectroscopy. The fatty acid composition ranged as follows: saturated fatty acids, C16:0 (palmitic) 11.3 to 31.8% and C18:0 (stearic) 5.7 to 8.7%, monounsaturated fatty acids, C18:1 (oleic) 21.8 to 35.7% and C18:1 trans isomers 0.4 to 27.4%, polyunsaturated fatty acid, C18:2 linoleic acid 5.2 to 40.2%. Some positional isomers of C18:1 as cis‐11‐octadecenoic acid varied from 0.7 to 4.6% and cis‐13 trace to 2.4%. The total trans fatty acid contents were between 0.9 and 32.0% when measured with capillary gas chromatography and between 0 and 30.2% with FT‐IR spectroscopy. Some of the margarines analyzed contained trace amount of trans fatty acids which could not be detected by FT‐IR spectroscopy.     

Comparison of fatty acid profiles and mid‐infrared spectral data for classification of olive oils

The composition of olive oils may vary depending on environmental and technological factors. Fatty acid profiles and Fourier‐transform infrared (FT‐IR) spectroscopy data in combination with chemometric methods were used to classify extra‐virgin olive oils according to geographical origin and harvest year. Oils were obtained from 30 different areas of northern and southern parts of the Aegean Region of Turkey for two consecutive harvest years. Fatty acid composition data analyzed with principal component analysis was more successful in distinguishing northern olive oil samples from southern samples compared to spectral data. Both methods have the ability to differentiate olive oil samples with respect to harvest year. Partial least squares (PLS) analysis was also applied to detect a correlation between fatty acid profile and spectral data. Correlation coefficients (R²) of a calibration set for stearic, oleic, linoleic, arachidic and linolenic acids were determined as 0.83, 0.97, 0.97, 0.83 and 0.69, respectively. Fatty acid profiles were very effective in classification of oils with respect to geographic origin and harvest year. On the other hand, FT‐IR spectra in combination with PLS could be a useful and rapid tool for the determination of some of the fatty acids of olive oils.     

Presence of Fatty‐Acid Ethyl Esters in Krill Oil Dietary Supplements

Krill oil dietary supplements are increasingly used for their high concentrations of phospholipids (PL), which offer reportedly greater bioavailability of n‐3 polyunsaturated fatty acids (PUFA) than those of triacylglycerols or fatty‐acid ethyl esters (FAEE) commonly found in fish oils and fish‐oil concentrates. This work evaluated the lipid composition of 22 commercial krill oil (CKO) supplements available in the US market, and found ten products (i.e. 45%) contained significant amounts of FAEE, varying from 41% to 75%, by weight. These concentrations of FAEE differed from the minor abundances of FAEE (<3%, by weight) found in manufacturer‐supplied krill oil. The potential clinical and regulatory implications for these findings warrant further investigation.     

Ahiflower oil: A novel non‐GM plant‐based omega‐3+6 source

Ahiflower oil, a novel and proprietary dietary oil with the richest effective combined essential fatty acids from a single non‐GM plant, has been developed agronomically in a unique vertically integrated “soil to oil” model at commercial scale by Nature's Crops International. Ahiflower oil helps resolve a persistent dilemma in sustainable global omega‐3 nutrition from marine sources while dramatically improving dietary omega‐3 EPA conversion from plant sources and while supplying beneficial anti‐inflammatory GLA not found in fish or algal oils. Having achieved key regulatory clearances in the US and EU, Ahiflower oil is launching in the latter half of 2015 in supplements and foods.     

Fatty Acid Profile of Sunshine Bass: II. Profile Change Differs Among Fillet Lipid Classes

Fatty acid (FA) profile of fish tissue mirrors dietary FA profile and changes in a time-dependent manner following a change in dietary FA composition. To determine whether FA profile change varies among lipid classes, we evaluated the FA composition of fillet cholesteryl esters (CE), phospholipids (PL), and triacylglycerols (TAG) of sunshine bass (SB, Morone chrysops x M. saxatilis) raised on feeds containing fish oil or 50:50 blend of fish oil and coconut, grapeseed, linseed, or poultry oil, with or without implementation of a finishing period (100% FO feed) prior to harvest. Each lipid class was associated with a generalized FA signature, irrespective of nutritional history: fillet PL was comprised largely of saturated FA (SFA), long-chain polyunsaturated FA (LC-PUFA), and total n-3 FA; fillet TAG was higher in MC-PUFA and total n-6 FA; and fillet CE was highest in monounsaturated FA (MUFA). Neutral lipids reflected dietary composition in a near-direct fashion; conversely, PL showed evidence of selectivity for MC- and LC-PUFA. Shorter-chain SFA were not strongly reflected within any lipid fraction, even when dietary availability was high, suggesting catabolism of these FA. FA metabolism in SB is apparently characterized by a division between saturated and unsaturated FA, whereby LC-PUFA are preferentially incorporated into tissues and SFA are preferentially oxidized for energy production. We demonstrated provision of SFA in grow-out feeds for SB, instead MC-PUFA which compete for tissue deposition, meets energy demands and allows for maximum inclusion of LC-PUFA within fillet lipids.     

Nondestructive Estimation of Fat Constituents of Sesame (Sesamum indicum L.) Seeds by Near‐Infrared Reflectance Spectroscopy

A rapid and efficient method for oil constituent estimation in intact sesame seeds was developed through near‐infrared reflectance spectroscopy (NIRS) and was used to evaluate a sesame germplasm collection conserved in China. A total of 342 samples were scanned by reflectance NIR in a range of 950–1650 nm, and the reference values for oil content and fatty acid (FA) profiles were measured by Soxhlet and gas chromatograph methods. Useful chemometric models were developed using partial least squares regression with full cross‐validation. The equations had low standard errors of cross‐validation, and high coefficient of determination of cross‐validation (R_c²) values (>0.8) except for stearic acid (0.794). In external validation, r² values of oil and FA composition equations ranged from 0.815 (arachidonic acid) to 0.877 (linoleic acid). The relative predictive determinant (RPD_v) values for all equations were more than 2.0. The whole‐seed NIR spectroscopy equations for oil content and FA profiles can be used for sesame seed quality rapid evaluation. The background information of the 4399 germplasm resources and accessions with high linoleic acid content identified in this study should be useful for developing new sesame cultivars with desirable FA compositions in future breeding programs.     

Microwave-Assisted,Base-Catalyzed Synthesis of Fatty Acid Methyl Esters from Seeds and Fish Oil Supplements

Growing health awareness has resulted in the increased use of dietary supplements derived from plants and marine sources, leaving consumers unsure of their best options. There were three objectives of the present study. The first was to design and evaluate an efficient derivatization procedure. The second was to perform a comparative analysis of liquid oils and their corresponding capsules of hemp, chia, and flax seeds. The final objective was to determine the fatty acid (FA) composition of six fish oil products and compare it to the one provided on the label. For the FA profiling, we implemented two efficient, one-step, sustainable methods with high percentage recovery for the synthesis of FA methyl esters (FAME), which use base catalysis and microwave-assisted heating. Our results found no difference in nutritional value between liquid oils and capsules of the seed supplements, with flaxseed and chia offering a higher, beneficial n-3:n-6 ratio compared to hemp oil. Four of the fish oils analyzed contained significantly less eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) than their reported label, and the other two not only agreed with the manufacturers' declaration but were able to fulfill the daily adequate intake (AI) with fewer capsules.     

Effect of low-to-moderate amounts of dietary fish oil on neutrophil lipid composition and function

Although essential to host defense, neutrophils are also involved in numerous inflammatory disorders including rheumatoid arthritis. Dietary supplementation with relatively large amounts of fish oil [containing >2.6 g eicosapentaenoic acid (EPA) plus 1.4 g docosahexaenoic acid (DHA) per day] can attenuate neutrophil functions such as chemotaxis and superoxide radical production. In this study, the effects of more moderate supplementation with fish oil on neutrophil lipid composition and function were investigated. The rationale for using lower supplementary doses of fish oil was to avoid adverse gastrointestinal problems, which have been observed at high supplementary concentrations of fish oil. Healthy male volunteers aged <40 yr were randomly assigned to consume one of six dietary supplements daily for 12 wk (n=8 per treatment group). The dietary supplements included four different concentrations of fish oil (the most concentrated fish oil provided 0.58 g EPA plus 1.67 g DHA per day), linseed oil, and a placebo oil. The percentages of EPA and DHA increased (both P<0.05) in neutrophil phospholipids in a dose-dependent manner after 4 wk of supplementation with the three most concentrated fish oil supplements. No further increases in EPA or DHA levels were observed after 4 wk. The percentage of arachidonic acid in neutrophil phospholipids decreased (P<0.05) after 12 wk supplementation with the linseed oil supplement or the two most concentrated fish oil supplements. There were no significant changes in N-formyl-met-leu-phe-induced chemotaxis and superoxide radical production following the dietary supplementations. In conclusion, low-to-moderate amounts of dietary fish oil can be used to manipulate neutrophil fatty acid composition. However, this may not be accompanied by modulation of neutrophil functions such as chemotaxis and superoxide radical production.     

Dietary saturated and omega‐3 fatty acids affect growth and fatty acid profiles of Malaysian mahseer

The current study was conducted to determine optimal levels of dietary saturated fatty acids (SFA), n‐3 PUFA and to study potential n‐3 sparing effect of dietary SFA for Malaysian mahseer Tor tambroides. Juvenile T. tambroides were fed four trial diets with similar basal composition but different oil mixtures in a 2 × 2 factorial experimental design for 10 weeks. The two factors were the levels of dietary SFA and the levels of dietary n‐3 PUFAs. Growth performance and fatty acid profile of tissues were analyzed at the end of the experiment. Significant differences in growth performance were observed among treatments, and fish fed the diet low in n‐3 and high in SFA showed the best growth performance. T. tambroides fed the high n‐3 diets showed a significantly higher (p<0.05) muscle total n‐3 PUFA content compared to fish fed the low n‐3 diets. The highest 22:6 n‐3 and total n‐3 PUFA content of the liver were also observed in fish fed the low n‐3 and high SFA diet. However, the significant interaction (p<0.05) between dietary SFA and n‐3 PUFA levels was observed for the total n‐3 PUFA content of both muscle and liver tissues, suggesting an n‐3 sparing action by dietary SFA. The results of this study suggest that 2.5% n‐3 PUFA in the diet of T. tambroides, with an SFA to n‐3 ratio of 15.3, is sufficient to provide the best growth performance and to retain the n‐3 content of tissues. Practical applications: The continuous increase of world population and growth of aquaculture industry put severe pressure on the marine resources such as fish oil and fishmeal. Here we show that fish oil can be substituted with palm oil, a cheaper and more available source of oil in tropical countries, in the diet of Malaysian mahseer without a reduction of growth. Moreover, palm oil as a source of SFA may spare omega‐3 in the fish tissues. Omega‐3 is an essential fatty acid for humans as final consumer of edible fish.     

Development and commercialization of GLA safflower oil

GLA safflower oil is a new commercial source of gamma‐linolenic acid (GLA), an important dietary omega‐6 fatty acid with properties similar and complementary to those of docosahexaenoic acid (DHA) and eicosapentaenoic acid (EPA). In its native form, GLA safflower oil contains 60–70+% GLA. It is one of the first dietary supplements developed using modern biotechnology methods and is the first of a new generation of genetically modified (GM) plant oil ingredients developed solely for improvement of human health and nutrition.     

Influence of different fats in pig feed on fatty acid composition of phospholipids and physical meat quality characteristics

Two feeding experiments (i, ii) were conducted to investigate the influence of different dietary fats on the fatty acid (FA) composition of phospholipids as well as meat quality in pigs. In each experiment 12�4 siblings of Swiss Landrace or Large White breed were allocated to one of four feeding treatments according to sex, breed, and litter and fattened from about 25 to 105 kg liveweight. Pigs were fed a control diet (barley, wheat, soybean meal) or the control diet supplemented with 7% pork fat, 4.95% olive oil or 3.17% soybean oil (i) or 5% of olein or stearin fraction of pork fat or hydrogenated fat (ii). The dietary FA composition was reflected in the FA composition of phospholipids in M. long. dorsi and triceps brachii. However, the unsaturated to saturated ratio was not affected by the dietary intake of polyunsaturated FAs and was only slightly increased by the olive oil supplementation. Trans FAs including conjugated linoleic acid were incorporated into phospholipids only to a small extent. The dietary altered fatty acid composition of phospholipids did not cause any effect on pH, cooking loss, texture, or colour of pork, but meat quality as well as the proportion of saturated FA, arachidonic acid, and n‐3 fatty acids were significantly influenced by genetic effects.     

Catalytic performance of Brønsted acid sites during esterification of acetic acid with ethyl alcohol over phosphotungestic acid supported on silica

Different ratios of phosphotungestic acid supported on silica gel were prepared by an impregnation method with PWA loadings ranging from 1 to 30% w/w and calcined at 350 and 500 °C for 4 h in a static air atmosphere. The catalysts were characterized by thermogravimety (TG), differential thermal analysis (DTA), X‐ray diffraction, FT‐IR spectroscopy and N₂ adsorption measurements. The surface acidity and basicity of the catalyst were investigated by the dehydration–dehydrogenation of isopropanol and the adsorption of pyridine (PY) and 2,6‐dimethyl pyridine (DMPY). The gas‐phase estrification of acetic acid with ethanol was carried out at 185 °C in a conventional fixed‐bed reactor at 1 atm using air as carrier gas. The results clearly revealed that the catalyst containing 10% w/w PWA/SiO₂ is the most active and delivers reaction selectively to ester with 85% yield. The Brønsted acid site resulting from hydroxylation of tungsten oxide plays the main role in the formation of ester. Copyright © 2007 Society of Chemical Industry     

Determination and Structural Elucidation of Triacylglycerols in Krill Oil by Chromatographic Techniques

The content of triacylglycerols (TAG) in krill oil is generally omitted from the labels of commercial supplements and unacknowledged in studies aimed at proving its health benefits. The present study demonstrates that TAG compounds, in addition to phospholipids and lysophospholipids, are an important lipid class in pure krill oil. The fatty acid composition of TAG molecules from krill oil and their distribution on the backbone of TAG structures were determined by gas chromatography and liquid chromatography tandem mass spectrometric, respectively. The content of omega 3 polyunsaturated fatty acids (n-3 PUFA) was similar to those reported in the literature for fish oil. It was estimated that 21 % of n-3 PUFA were at the sn-2 position of TAG structures. To our knowledge, this is the first determination and structural characterization of TAG in pure krill oil supplements.     

Determining Ethyl Esters in Fish Oil with Solid Phase Microextraction and GC–MS

The long-chain polyunsaturated fatty acids (PUFA) found in fish oil, specifically eicosapentanoic acid (EPA) and docosahexanoic acid (DHA) play an important part in human health. As a result, fish oil supplements are commonly consumed by people around the world. Supplements in the form of triacylglycerols (TAG) can be sold at a premium price, compared to those in the ethyl ester (EE) forms. Producers of TAG supplements require a simple, rapid method to determine the authenticity of their raw material. Here, we describe a method to quantify EE in fish oil using solid phase microextraction headspace analysis and GCMS. Despite the variation in linear ranges of the calibration curves with volatility of the EE, 30 individual FA were quantified including common saturated FA such as palmitic and stearic acid, as well as longer chain PUFA, such as EPA and DHA. The method was then applied to three commercial fish oils in the TAG form and two of the products were found to contain EE, with one containing EE above 1.5% w/w, indicating that contamination had occurred. With growing consumer interest in fish oil products, the method proposed here will help resolve future issues of authenticity in fish oils.     

Fatty Acid Profile of Sunshine Bass: I. Profile Change is Affected by Initial Composition and Differs Among Tissues

Fatty acid (FA) composition of fillet tissue can be tailored by transitioning fish from alternative lipid-based, low long-chain polyunsaturated fatty acid (LC-PUFA) grow-out feeds to high LC-PUFA "finishing" feeds. To address whether grow-out feed composition influences the responsiveness of fillet tissue to finishing, sunshine bass (SB, Morone chrysops x M. saxatilis) were reared to a submarketable size on grow-out feeds containing fish oil (FO) or a 50:50 blend of FO and coconut (CO), grapeseed (GO), linseed (LO), or poultry (PO) oil. For the final 8 weeks of the trial, fish were either maintained on assigned grow-out feeds or finished with the 100% FO feed. Production performance was unaffected by dietary lipid source, but fillet FA profile generally conformed to nutritional history. Regardless of grow-out regimen, finishing had a significant restorative effect on fillet FA composition; however, complete restoration of control levels of 20:5n-3, 22:6n-3, total LC-PUFA and n-3:n-6 FA ratio was achieved only among fish fed the CO-based grow-out feed. Saturated fatty acids (SFA) appear to be preferential catabolic substrates, whereas medium-chain and long-chain PUFA are selectively deposited in tissues. Provision of SFA in grow-out feeds appears to optimize selective FA metabolism and restoration of beneficial fillet FA profile during finishing.     

Rapid Assessment of Quality Parameters in Cocoa Butter Using ATR-MIR Spectroscopy and Multivariate Analysis

The development of sensitive and robust screening tool(s) for assuring the quality of incoming raw materials would supplement the assurances provided by food manufacturer vendor auditing programs. Our aim was to evaluate the ability of attenuated total reflectance mid‐infrared (ATR‐MIR) spectroscopy in combination with multivariate analysis as a screening tool for the diverse cocoa butter supply. Forty different cocoa butter samples encompassing an acceptable range of compositional variability for the chocolate industry were included. Cocoa butters were characterized for their melt characteristics (melting heat), triacylglycerol content and fatty acid composition (GC‐FAME). Soft independent modeling of class analogy (SIMCA) and partial least squares regression (PLSR) were used for classification and quantification analysis. SIMCA classified all cocoa butters in distinct clusters in a 3‐dimensional space but no sample clustering patterns were associated with melt characteristics. Spectral differences responsible for the separation of classes were attributed to stretching vibrations of the ester (–C=O) linkage (1,660–1,720 cm^?1). PLSR models showed correlation coefficients >0.93 and prediction errors (SECV) of 1.5 units for melt characteristics, 0.2–0.3 and 0.4–0.8 % for major fatty acids and triacylglycerols, respectively. ATR‐MIR spectroscopy combined with pattern recognition analysis provides robust models for characterization and determination of cocoa butter composition.     

Efficient Synthesis of Octacosanol Linoleate Catalyzed by Ionic Liquid and Its Structure Characterization

Octacosanol, as the major active policosanol, has attracted much attention due to the potential beneficial effects for human health. However, free octacosanol has a high melting point, poor oil solubility and low bioavailability, which greatly restricts its practical application. In this study, we report a highly efficient method for an ionic liquids (IL)‐catalyzed synthesis of octacosanol ester by direct esterification with linoleic acid. The synthesized product was purified, subsequently characterized by FT‐IR, MS and NMR and finally confirmed to be octacosanol linoleate. The reaction parameters were investigated and the conversion reached 91.3 ± 4.8 % under the optimum conditions: IL 1‐butylsulfonate‐3‐methylimidazolium hydrogen sulfate ([BSO₃HMim][HSO₄]) as catalyst, IL dose 1.5 % (related to the mass of both reactants), 1:1 molar ratio of octacosanol to linoleic acid, 80 °C, and 1 h. The melting point and oil solubility of octacosanol were greatly improved by esterification with linoleic acid, facilitating the incorporation into a variety of oil‐based systems.     

Synthesis of a self‐emulsifiable waterborne epoxy curing agent based on glycidyl tertiary carboxylic ester and its cure characteristics

A novel self‐emulsifiable waterborne amine‐terminated curing agent for epoxy resin based on glycidyl tertiary carboxylic ester (GTCE) was synthesized through three steps of addition reaction, capping reaction, and salification reaction of triethylene tetramine (TETA) and liquid epoxy resin (E‐44). The curing agent with good emulsifying and curing properties was gradually obtained under condition of the molar ratio of TETA: E‐44 as 2.2: 1 at 65 °C for 4 h, 100% primary amine capped with GTCE at 70 °C for 3 h, and 20% salifiable rate with glacial acetic acid. The curing agent was characterized by Fourier transform‐infrared spectroscopy (FT‐IR). The curing behavior of the E‐44/GTCE‐TETA‐E‐44 system was studied with differential scanning calorimetry (DSC) and FT‐IR. Results showed that the optimal mass ratio for E‐44/GTCE‐TETA‐E‐44 system was 3 to 1, and the curing agent showed a relatively lower curing temperature. The cured film prepared by the self‐emulsifiable curing agent and epoxy resin under the optimal mass ratio displayed good thermal property, hardness, toughness, adhesion, and corrosion resistance. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44246.