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1.
A generalized partial-least-squares calibration for determination of the trans content of edible fats and oils by Fourier transform near-infrared (FT-NIR) spectroscopy using 8-mm disposable glass vials for sample handling and measurement was developed. The trans contents of a broad range of oils were determined using the American Oil Chemists' Society single-bounce horizontal attenuated total reflectance (SB-HATR) mid-infrared spectroscopic procedure, these trans reference data were used in the development of the generalized FT-NIR calibration. Additional refined and product-specific calibrations were also developed, and all the calibrations were assessed for their predictive capabilities using two sets of validation samples, one comprising a broad range of oil types and the other restricted to oils with specific characteristics. The FT-NIR trans predictions obtained using the generalized calibration were in good agreement with the SB-HATR results; the values were accurate and reproducible to within ±1.1 and ±0.5% trans, respectively, compared to a reproducibility of ±0.40% trans obtained for the SB-HATR method. The accuracy of the predictions obtained from the generalized FT-NIR calibration for particular oil types was not significantly improved by supplementing the base training set with samples of these specific types. Calibrating only these oil types did, however, produce a substantial improvement in predictive accuracy, aproaching that of the SB-HATR method. These product specific calibrations produced serious predictive errors when nonrepresentative samples were analyzed. The incorporation of a supplementary discriminate analysis routine was found to be a powerful safeguard in flagging nonrepresentative samples as outliers and could also be used to select the calibration most appropriate for the characteristics of the sample being analyzed. Overall, it was concluded that FT-NIR spectroscopy provides a viable alternative to the SB-HATR/mid-Fourier transform infrared method for trans determination, making use of more industrially robust instrumentation and equipped with a simpler sample handling system.  相似文献   

2.
A Fourier transform infrared (FTIR) edible oil analysis package designed to simultaneously analyze for trans content, cis content, iodine value (IV), and saponification number (SN) of neat fats and oils by using calibrations based on pure triglycerides and derived by application of partial-least-squares (PLS) regression was assessed and validated. More than 100 hydrogenated rapeseed and soybean samples were analyzed by using the edible oil analysis package as well as the newly proposed modification of the AOCS IR trans method with trielaidin in a trans-free oil as a basis for calibration. In addition, ∼1/3 of the samples were subsequently reanalyzed by gas chromatography (GC) for IV and trans content. The PLS approach predicted somewhat higher trans values than the modified AOCS IR method, which was traced to a combination of the inclusion of trilinolelaidin in the calibration set and the effects of baseline fluctuations. Eliminating trilinolelaidin from the triglyceride standards and the use of second-derivative spectra to remove baseline fluctuations produced excellent concurrence between the PLS and modified AOCS IR methods (mean difference of 0.61% trans). Excellent internal consistency was obtained between the IV and cis and trans data provided by the edible oil analysis package, and the relationship was close to that theoretically expected [IV=0.86 (cis + trans)]. The IV data calculated for the GC-analyzed samples matched the PLS IV predictions within 1 IV unit. The trans results obtained by both IR methods were linearly related to the GC data; however, as is commonly observed, the GC values were significantly lower than the IR values, the GC and IR data being related by a slope factor of ∼0.88, with an SD of ∼0.80. The concurrence between the trans data obtained by the two FTIR methods, and between the FTIR and GC-IV data, as well as the internal consistency of the IV, cis and trans FTIR predictions, provides strong experimental evidence that the edible oil analytical package measures all three variables accurately. Co-Director, McGill IR Group.  相似文献   

3.
A method for the simultaneous determination of iodine value (IV) and trans content from the Fourier transform infrared (FTIR) spectra of neat fats and oils recorded with the use of a heated single-bounce horizontal attenuated total reflectance (SB-HATR) sampling accessory was developed. Partial least squares (PLS) regression was employed for the development of the calibration models, and a set of nine pure triacylglycerols served as the calibration standards. Regression of the FTIR/PLS-predicted IV and trans contents for ten partially hydrogenated oil samples against reference values obtained by gas chromatography yielded slopes close to unity and SD of <1. Good agreement (SD<0.35) also was obtained between the trans predictions from the PLS calibration model and trans determinations performed by the recently adopted AOCS FTIR/SBHART method for the determination of isolated trans isomers in fats and oils.  相似文献   

4.
A rapid Fourier transform infrared (FTIR) method was developed to simultaneously determine percentcis andtrans content of edible fats and oils. A generalized, industrial sample-handling platform/accessory was designed for handling both fats and oils and was incorporated into an FTIR spectrometer. The system was calibrated to predict thecis andtrans content of edible oils by using pure triglycerides as standards and partial least squares as the chemometric approach. The efficacy of the calibration was assessed by triglyceride standard addition, by mixing of oils with varyingcis/trans contents, and by analyzing fats and oils of known iodine value. Each of the approaches verified that the FTIR method measured thecis andtrans content in a reproducible (±0.7%) manner, with the measured accuracies being 1.5% for standard addition and 2.5% for the chemically analyzed samples. Comparisons also were made to the conventional American Oil Chemists’ Society (AOCS) method for the determination oftrans isomers by IR spectroscopy. The FTIR-partial least squares approach worked well over a wide range oftrans contents, including those between 0 and 15%. The sample-handling accessory designed for this application is robust, flexible, and easy to use, being particularly suited for quality-control applications. In addition, the analysis was automated by programming the spectrometer in Visual Basic (Windows), to provide a simple, prompt-based user interface and to allow an operator to carry outcis/trans analyses without any knowledge of FTIR spectroscopy. A typical analysis requires less than two minutes per sample. The derived calibration is transferable between instruments, eliminating the need for recalibration. The integrated analytical system provides a sound basis for the implementation of FTIR methods in place of a variety of AOCS wet chemical methods when analytical speed, cost, and environmental concerns are issues.  相似文献   

5.
Azizian H  Kramer JK 《Lipids》2005,40(8):855-867
A rapid method was developed for classifying and quantifying the FA composition of edible oils and fats using Fourier Transform near infrared spectroscopy (FT-NIR). The FT-NIR spectra showed unique fingerprints for saturated FA, cis and trans monounsaturated FA, and all n−6 and n−3 PUFA within TAG to permit qualitative and quantitative comparisons of fats and oils. The quantitative models were based on incorporating accurate GC data of the different fats and oils and FT-NIR spectral information into the calibration model using chemometric analysis. FT-NIR classification models were developed based on chemometric analyses of 55 fats, oils, and fat/oil mixtures that were used in the identification of similar materials. This database was used to prepare three calibration models—one suitable for the analysis of common fats and oils with low levels of trans FA, and the other two for fats and oils with intermediate and high levels of trans FA. The FT-NIR method showed great potential to provide the complete FA composition of unknown fats and oils in minutes. Compared with the official GC method, the FT-NIR method analyzed fats and oils directly in their neat form and required no derivatization of the fats to volatile FAME, followed by time-consuming GC separations and analyses. The FT-NIR method also compared well with the official FTIR method using an attenuated total reflectance (ATR) cell; the latter provided only quantification of specific functional groups, such as the total trans FA content, whereas FT-NIR provided the complete FA profile. The FT-NIR method has the potential to be used for rapid screening and/or monitoring of fat products, trans FA determinations for regulatory labeling purposes, and detection of contaminants. The quantitative FT-NIR results for various edible oils and fats and their mixtures are presented based on the FT-NIR model developed.  相似文献   

6.
An automated protocol for the direct, rapid determination of isolated trans content of neat fats and oils by Fourier transform infrared (FTIR) spectroscopy was devised, based on a simple modification of the standard AOCS trans method, eliminating the use of CS2 and methylation of low trans samples. Through the use of a commercially available, heated transmission flow cell, designed specifically for the analysis of neat fats and oils, a calibration (0–50%) was devised with trielaidin spiked into a certified, trans-free soybean oil. The single-beam spectra of the calibration standards were ratioed against the single-beam spectrum of the base oil, eliminating the spectral interference caused by underlying triglyceride absorptions, facilitating direct peak height measurements as per the AOCS IR trans method. The spectrometer was preprogrammed in Visual Basic to carry out all spectral manipulations, measurements, and calculations to produce trans results directly as well as to provide the operator with a simple interface to work from. The derived calibration was incorporated into the software package, obviating the need for further calibration because the program includes an automatic recalibration/standardization routine that automatically compensates for differences in optical characteristics between instruments, instrument drift over time, and cell wear. The modified AOCS FTIR analytical package was evaluated with Smalley check samples for repeatability, reproducibility, and accuracy, producing SD of ± 0.07, 0.13, and 0.70 trans, respectively, the FTIR predictions being linearly related to the Smalley means (r=0.999; SD=± 0.46), and well within one SD of the Smalley sample means. Calibration transfer was assessed by implementing the calibration on a second instrument and reanalyzing the Smalley check samples in cells of two different pathlengths (25- and 50-μm). There were no statistically significant differences between the FTIR trans predictions obtained for the Smalley samples from the two instruments and two cells, indicating that the software was able to adjust the calibrations to compensate for differences in instrument response and cell pathlength. The FTIR isolated trans analysis protocol developed by the McGill IR Group has the benefit of being based on the principles of an AOCS-approved method, matches its accuracy, and allows the analysis to be performed on both neat fats and oils, producing trans predictions in less than 2 min per sample. It is suggested that this integrated approach to trans analysis, which requires a minimum level of sample manipulation and operator skill, be considered as a modification of the proposed Recommended Practice CD14b-95.  相似文献   

7.
This work demonstrates the application of partial least squares (PLS) analysis as a discriminant as well as a quantitative tool in the analysis of edible fats and oils by Fourier transform near-infrared (FT-NIR) spectroscopy. Edible fats and oils provided by a processor were used to calibrate a FT-NIR spectrometer to discriminate between four oil formulations and to determine iodine value (IV). Samples were premelted and analyzed in gass vials maintained at 75°C to ensure that the samples remained liquid. PLS calibrations for the prediction of IV were derived for each oil type by using a subset of the samples provided as the PLS training set. For each oil formulation (type), discrimination criteria were established based on the IV range, spectral residual, and PLS factor scores output from the PLS calibration model. It was found that all four oil types could be clearly differentiated from each other, and all the validation samples, including a set of blind validation samples provided by the processor, were correctly classified. The PLS-predicted IV for the validation samples were in good agreement with the gas chromatography IV values provided by the processor. Comparable predictive accuracy was obtained from a calibration derived by combining samples of all four oil types in the training set as well as a global IV calibration supplied by the instrument manufacturer. The results of this study demonstrate that by combining the rapid and convenient analytical capabilties of FT-NIR spectroscopy with the discriminant and predictive power of PLS, one can both identify oil type, as well as predict IV with a high degree of confidence. These combined capabilities provide processors with better control over their process.  相似文献   

8.
A method for the determination of iodine value (IV) by Fourier transform-near infrared (FT-NIR) spectroscopy was developed and evaluated in an international collaborative study. The FT-NIR analyzer employed in this work uses disposable vials for sample handling and incorporates validation protocols designed to ensure that the calibration will give accurate results from analyzer to analyzer and stability over time without any further calibration development work. The global IV calibration was developed from over 1,200 animal, marine, and vegetable oils and fats, which were obtained on a number of different instruments worldwide. The Standard Error of Cross Validation measured from a range of 0–190 IV varied from ±0.2–1.4 IV (1 sigma). The repeatability for all models was on the order of 0.1 IV, which states that most of the error was inherited from the primary methods. Finally, an international interlaboratory study was carried out with 16 samples obtained from the AOCS Smalley Laboratory Proficiency Program and an oil processor. The average reproducibility error in any one lab was better than 0.15, and the average reproducibility between labs was better than 0.33. An uncertainty of 0.45 was calculated from the average FT-NIR values obtained from the collaborative study vs. the AOCS Certified Wijs method (Cd 1d-92).  相似文献   

9.
A Fourier transform infrared spectroscopic procedure was used to analyze 34 edible fats (22 shortenings and 12 vegetable margarines) as neat fats (IRNF) to determine their total trans fatty acid (TFA) content. The sloping baseline was corrected with a reference spectrum based on a nonprocessed olive oil. The calibration was done using seven partially hydrogenated fats with an individual TFA content previously determined by the combination of gas chromatography (GC) with argentation thin-layer chromatography. Taking into account the different absorptivities of various trans isomers, different correction factors were calculated using the calibration standards (0.83 and 1.71 for single trans bonds in both diethylene and triethylene and for trans, trans-diethylene fatty acids, respectively) and applied to calculate the total TFA of samples. Moreover, the samples were converted to their methyl esters and reanalyzed following the same procedure (IRFAME). Differences in TFA content of fats were not found when a t-test was used to compare the results obtained by IRNF vs. either IRFAME or GC, suggesting that IR of neat fats could be used, thus avoiding the need to prepare sample solutions in organic solvents and to prepare fatty acid methyl esters. The mean TFA content (determined by IRNF) of a representative group of Spanish shortenings (22 samples) that varied widely in terms of fat sources, processes, and purposes (bakery, sandwiches, ice cream, coatings, chocolate coverings) was 6.55±11.40%, although more than 54% contained <3% of TFA. Fatty acid composition of shortenings by direct GC using a 100-m polar cyanopolysiloxane capillary column indicated that the mean trans-18∶2 isomer content was 0.58%, ranging from 0.9 to 3.4%. Small amounts of trans-18∶3 isomers (<0.3%) were observed in 18 of the 22 shortenings studied; the maximal value was <2%. The mean value of the fraction saturated+TFA of shortenings was high (59.95±12.73%), including two values higher than 83%.  相似文献   

10.
A Fourier transform infrared spectroscopy procedure is described for quantitating the levels of totalrans triglycerides or their fatty acid methyl ester derivatives in neat fats and oils. It requires either warming or no preparation of the laboratory sample, and about 5 min for spectroscopic measurement, band area integration, and calculation of thetrans content from a linear regression equation. To eliminate the strongly sloping background of the 966-cm−1 trans band, the single-beam spectrum of thetrans-containing fat is “ratioed” against that of an unhydrogenated oil or a reference material that contains onlycis double bonds. Thus, a symmetric absorption band on a horizontal background is obtained. The area under thetrans band can then be accurately integrated between the same limits, 990 and 945 cm−1, for alltrans levels investigated. To speed up the analysis, an attenuated total reflection liquid cell was used, into which oils, melted fats or their methyl esters were poured without weighing or quantitative dilution with the toxic and volatile carbon disulfide solvent. Thetrans levels determined by attenuated total reflection were closer to those found by capillary gas chromatography when the hydrogenated fat was measured against the corresponding unhydrogenated oil than when it was measured against acis reference material. Small differences were found betweentrans levels in hydrogenated fat test samples and the corresponding methyl ester derivatives (9.3 and 2.2% at about 2 and 41%trans, respectively). The lower limits of identification and quantitation were 0.2 and 1%, respectively.  相似文献   

11.
Trans FA (TFA), solid fat contents (SFC), and slip melting points of 12 different tub and stick margarines marketed in Turkey were examined in this study. No trans isomers were found in four margarines, which suggests they were formulated from interesterified or blended fats and oils. The products with no TFA generally had more short-chain saturated FA, which suggests coconut oil-based oil components. TFA content of the other 10 products varied from 7.7 to 37.8%. Compared to the products formulated in North America, Turkish margarines contain more TFA and have higher SFC.  相似文献   

12.
Silver-phase high-performance liquid chromatography (HPLC) on silver nitrate-loaded silica achieves incomplete separation of major triacylglycerol (TAG) classes present intrans-hardened fats. The “ChromSpher Lipids” silverloaded cation exchange HPLC column has been found to yield good separations oftrans-hardened TAG, with molecular species well resolved. Separations comparable to those previously possible for nonhardened fats are now possible fortrans-hardened fats. The separation is on the basis of number and type (i.e.cis/trans) of double bonds only; the position of the double bond along the acyl group appears not to influence the separation significantly. The analysis of a palm fraction, hardened to a slip melting point of 37°C and chemically randomized, is presented as an example. This technique offers a new approach to understanding and controlling the hydrogenation and processing oftrans-hardened fats.  相似文献   

13.
Declarations of the total content of trans fatty acids (FA) and saturated FA (SFA) are mandatory on food labels in the US and Canada. Gas chromatography (GC) has been the method of choice for the determination of FA composition. However, GC is time consuming and requires conversion of fats and oils to their FA methyl esters. In the present study, a recently published Fourier transform near-infrared (FT-NIR) spectroscopic procedure was applied to the rapid (<5 min) determination of total SFA, monounsaturated FA (MUFA), polyunsaturated FA (PUFA), and trans FA contents of 30 commercially available edible fats and oils. Good agreement was obtained between the GC and FT-NIR methods for the determination of total SFA, MUFA, and PUFA contents. Differences between the two methods were apparent for the determination of trans fat at trans fat levels <2 % of total fat. The analytical determinations of total SFA, MUFA, and PUFA contents for many of the oils examined differed from the respective values declared on the product labels. Our findings demonstrate that the FT-NIR procedure serves as a suitable alternative method for the rapid determination of total SFA, MUFA, PUFA and trans FA contents of neat vegetable oils.  相似文献   

14.
The AOCS Official Method Ce 1h-05 was recently approved at the 96th AOCS Annual Meeting (2005) by the Uniform Methods Committee as the official method for determining cis and trans FA in vegetable or non-ruminant fats and oils. A series of experiments was undertaken using a margarine (hydrogenated soybean oil) sample containing approximately 34% total trans FA (28% 18∶1 trans, 6% 18∶2 trans, and 0.2% 18∶3 trans), a low-trans oil (ca. 7% total trans FA), and a proposed system suitability mixture (12∶0, 9c−18∶1, 11c−18;1, 9c,12c,15c−18∶3, 11c−20∶1, and 21∶0) in an effort to evaluate and optimize the separation on the 100-m SP-2560 and CP-Sil 88 flexible fused-silica capillary GC columns recommended for the analysis. Different carrier gases and flow rates were used during the evaluation, which eventually lead to the final conditions to be used for AOCS Official Method Ce 1h-05.  相似文献   

15.
This study examined trans monounsaturated fatty acid contents in all margarines and shortenings marketed in Denmark, and in frying fats used by the fast-food restaurants Burger King and McDonald’s. Trans C18:1 content was 4.1±3.8% (g per 100 g fatty acids) in hard margarines, significantly higher than the content in soft margarines of 0.4±0.8%. Shortenings had an even higher content of trans C18:1, 6.7±2.3%, than the hard margarines. Margarines and shortenings with high contents of long-chain fatty acids had about 20% total trans monoenoic of which close to 50% were made up of trans long-chain fatty acids. Both fast-food frying fats contained large amounts of trans C18:1, 21.9±2.9% in Burger King and 16.6±0.4% in McDonald’s. In Denmark the per capita supply of trans C18:1 from margarines and shortenings and frying fats has decreased steadily during recent years. The supply of trans C18:1 from margarines and shortenings in the Danish diet is now 1.1 g per day.  相似文献   

16.
Fourier transform near-infrared (FT-NIR) spectroscopy in conjunction with partial least squares 1 (PLS1) calibration models was previously reported to be an alternative method to GC for the rapid determination of the fatty acid (FA) composition of fats and oils. These calibration models had been developed based on accurate GC data (primary reference method) and observed FT-NIR spectra. In the present three-laboratory limited collaborative study, the transferability of these pre-developed calibration models to four other FT-NIR spectrometers from the same manufacturer was evaluated. Six samples were selected that provided a wide range of FA contents. Our results indicate that these models were successfully transferable to spectrometers operating in the transflection mode with 2- or 4-mm pathlength fiber optic probes or in the transmission mode using 5-mm, but not 8-mm, outer diameter tubes. The predicted FA composition fell within the statistically accepted limits of agreement between FT-NIR and GC. The FT-NIR precision data were consistent with those reported in a published GC collaborative study. The application of FT-NIR to the determination of the total content of SFA, trans FA, MUFA, and PUFA is cost-effective and potentially suitable for the rapid screening of commercial products for compliance verification with labeling regulations.  相似文献   

17.
This study examined trans monounsaturated fatty acid contents in all margarines and shortenings marketed in Denmark, and in frying fats used by the fast-food restaurants Burger King and McDonald’s. Trans C18:1 content was 4.1±3.8% (g per 100 g fatty acids) in hard margarines, significantly higher than the content in soft margarines of 0.4±0.8%. Shortenings had an even higher content of trans C18:1, 6.7±2.3%, than the hard margarines. Margarines and shortenings with high contents of long-chain fatty acids had about 20% total trans monoenoic of which close to 50% were made up of trans long-chain fatty acids. Both fast-food frying fats contained large amounts of trans C18:1, 21.9±2.9% in Burger King and 16.6±0.4% in McDonald’s. In Denmark the per capita supply of trans C18:1 from margarines and shortenings and frying fats has decreased steadily during recent years. The supply of trans C18:1 from margarines and shortenings in the Danish diet is now 1.1 g per day.  相似文献   

18.
Seed oils were extracted with n-hexane from three edible Leguminosae seeds: Tylosema esculentum, Xanthocercis zambesiaca, and Bauhinia petersiana, giving yields of 48.2, 17.6, and 20.8% (w/w), respectively. Some physical and chemical parameters were determined to ascertain the general characteristics of the oils. The saponification and iodine values indicated that all three oil samples could be classified among the olive group of oils. This inference was supported by the results of the detailed fatty acid composition of the oils as determined by capillary gas chromatography. The ratio of total unsaturated to total saturated fatty acids in all three oil samples was approximately 70:30, with either oleic or linoleic acid being the dominant fatty acid. These results were in agreement with a proton nuclear magnetic resonance analysis of the fatty acid classes in the seed oils. Thus, the analysis served to justify the use of the three Leguminosae seed oils in food preparations. The work has further indicated that, with their attractive properties, the seed oils from T. esculentum, X. zambesiaca, and B. petersiana are good candidates for further studies to evaluate their future commercial prospects in the Southern African region.  相似文献   

19.
The fatty acid composition of twelve French tub margarines and three industrial shortenings was established with particular attention to theirtrans-18:1 acid content. Four of the twelve margarines (including two major brands, with 60% of market share) were devoid oftrans isomers, one contained less than 2%trans-18:1 acids, whereas the seven others had a mean content of 13.5 ± 3.6%trans isomers. Four years ago, no margarines with 0%trans-18:1 acids could be found. It is deduced that the recent Dutch and American studies on possible effects oftrans acids on human health (serum cholesterol, heart disease risks) may have had some influence on French margarine manufacturers. Presently, an average French tub margarine contains only 3.8% oftrans-18:1 acids instead of 13% four years ago. To protect brand names, some manufacturers have replaced partially hydrogenated oils with tropical fats or fully hydrogenated oils. On the other hand, two of the three shortenings had high levels oftrans-18:1 acids: 53.5 and 62.5%. This last value, obtained for a sample of hydrogenated arachis oil, seems to be one of the highest values ever reported for edible hydrogenated oils. In this sample,trans-18:1 plus saturated acids accounted for 85% of total fatty acids. This would indicate that shortening producers and users are not yet aware of recent dietary recommendations, probably because these products are not easily identifiable by consumers in food items, in contrast to margarines.  相似文献   

20.
The contents of total trans FA of sunflower oils at different stages of refining processes were determined by capillary GLC. The contents of 18∶1, 18∶2, and 18∶3 trans acids were 0.22±0.03, 2.31±0.23, and 0.03±0.01%, respectively, in physically refined sunflower oils, and 0.05±0.01, 0.69±0.26, and 0.02±0.01%, respectively, in chemically refined sunflower oils. The total trans FA contents drastically increased at the end of the physical refining process. The total trans FA contents of chemically refined sunflower oils were <1%. Because of the high temperature applied in the last stage of physical refining, the content of total trans FA was higher than in chemically refined sunflower oils. The last-stage conditions should be carefully evaluated to reduce the formation of trans FA during physical refining.  相似文献   

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