Determination of the fatty acid composition of the oil in intact-seed mustard by near-infrared reflectance spectroscopy

Near-infrared reflectance spectroscopy (NIRS) was used to estimate the fatty acid composition of the oil in intact-seed samples of Ethiopian mustard (Brassica carinata Braun) within a mutation breeding program that produced seeds with variable fatty acid compositions. Five populations, from 1992 to 1996 crops, were included in this study; and NIRS calibration equations for major fatty acids (palmitic, stearic, oleic, linoleic, linolenic, eicosenoic, and erucic) were developed within each single population. Furthermore, global calibration equations, including samples from the five populations, were developed. After external validation, the NIRS technique permitted us to obtain a reliable and accurate nondestructive estimation of the fatty acid composition of the oil, especially for the major acids—oleic, linoleic, linolenic, and erucic. For these, the r ² in external validation was higher than 0.95 by using both single-and multipopulation equations, and higher than 0.85 for the remaining fatty acids. Moreover, the multipopulation equations provided an accurate estimation of samples from a population not represented in the calibration data set, with values of coefficient of determination in validation (r ²) from 0.80 (palmitic and eicosenoic acids) to 0.97 (erucic acid). The ability of NIRS to discriminate among different fatty acid profiles was mainly due to changes within six spectral regions, 1140–1240, 1350–1400, 1650–1800, 1880–1920, 2140–2200, and 2240–2380 nm, all of them associated with fatty acid absorbers. Thus, NIRS can be used to estimate the fatty acid composition of Ethiopian mustard seeds with a high degree of accuracy, provided that calibration equations be developed from calibration sets that include large variability for the fatty acid composition of the oil.     

Estimation of Protein and Fatty Acid Composition in Shell-Intact Cottonseed by Near Infrared Reflectance Spectroscopy

Rapid and accurate analysis of cottonseed protein content and the composition of fatty acids (especially, saturated fatty acids) is often required in cotton production and breeding programs. This study aimed to establish a set of effective estimation models for these parameters. Near infrared reflectance spectroscopy (NIRS) calibration equations using partial least-squares regression for protein concentration, oil concentration, and five fatty acids of shell-intact cottonseeds were established based on 90 varieties, and the prediction abilities of the calibration models were verified using 45 other varieties. The prediction abilities of the NIRS calibration equations were basically consistent with external validation results. Each equation was assessed based on the ratio of performance to deviation (RPD_p). Protein content and seed total fatty acid (STA) content had high RPD_p values (3.687 and 3.530, respectively), whereas cottonseed kernel total fatty acid (KTA) content, linoleic acid (18:2), stearic acid (18:0), myristic acid (14:0), and palmitic acid (16:0) exhibited relatively high RPD_p (2.866, 2.836, 2.697, 2.676, and 2.506, respectively). The calibration model for oleic acid (18:1) had a low RPD_p (1.945). The results indicated that NIRS can be used to rapidly determine contents of STA, KTA, protein, stearic acid (18:0), myristic acid (14:0), and palmitic acid (16:0) in shell-intact cottonseed.     

Measurement of fatty acids in whole soybeans with near infrared spectroscopy

Improvement of nutritional and/or functional properties of soybean oil by modification of soy fatty acid composition is one of the objectives of plant breeders. A major element of breeding is rapid identification and tracking of traits in seed samples. This discussion summarizes the progression of whole‐soybean fatty acid calibration developments at Iowa State University. Emphasis was placed on linolenic acid (18:3) and total saturates (16:0 + 18:0). Normal soybeans have 12–20% (of the oil) saturated fats; modified low saturate soybeans have 6–8% saturated fats. Normal soybeans have 6–12% linolenic acid; modified low linolenic soybeans have 1–3% linolenic acid. Infratec 122x/1241 and Bruins OmegaG NIRS units were calibrated to measure fatty acid levels as a percentage of total oil content, in whole soybeans. The first Infratec calibrations (in 1998) did not remain accurate as soybean genetics changed. Iterations of the calibration process yielded calibrations for total saturates and linolenic acid with standard errors of prediction (on 2005 crop samples not included in the calibration pool) of 1.0% percentage points and 0.8% points, respectively. These were sufficient to classify modified versus normal concentrations of the two fatty acids. The NIRS units could not determine the specific percentages within the classes of modified and normal soybeans.     

Opportunities and problems in modification of levels of rapeseed C18 unsaturated fatty acids

Selections for different levels of C₁₈ fatty acids in rapeseed to date have had only limited success, due in part to the low frequency of occurrence of desired genotypes with increased linoleic and decreased linolenic acid. In the progeny of mutation experiments with seeds of the variety Oro (linolenic acid content 8–10%) two stable mutants were selected, one with 5% and the other with 20% linolenic acid in the seed oil. The level of linoleic acid in the two mutants is the same as Oro (16–20%), but the levels of oleic and linolenic acids are inversely altered. In this paper several problems associated with selecting for linoleic and linolenic acids, which became apparent during the mutation studies, are discussed. Many selections made from the mutated material were unstable, reverting to the original Oro fatty acid composition after two or three self-pollinated generations. This fact plus environmental and maternal effects made selection difficult. However, with the use of rapid and simple analytical methods and space-saving growing techniques, these difficulties were overcome. One of six papers presented in the symposium “Rapeseed Marketing and Breeding,” AOCS Meeting, Ottawa, September 1972.     

Near‐infrared spectroscopy for analysis of oil content and fatty acid profile in almond flour

Almond kernels show large variability for oil content and fatty acid profile. The objective of this research was to evaluate the potential of near infrared (NIR) reflectance spectroscopy (NIRS) for the analysis of these traits in almond flour. Ground kernels of 181 accessions collected in 2009 were used for developing calibration equations for oil content and concentrations of individual fatty acids. Calibration equations were developed using second derivative transformation and modified partial least squares regression. They were validated with samples from 179 accessions collected in 2010. The accuracy of calibration equations was measured through the coefficient of determination (r²) in external validation and the ratio of the SD in the validation set to the standard error of prediction (RPD). Both r² and RPD were high for oil content (r² = 0.99; RPD = 9.24) and concentrations of oleic (r² = 0.97; RPD = 5.37) and linoleic acids (r² = 0.98; RPD = 7.35), revealing that calibration equations for these traits are highly accurate. Conversely, the accuracy of the calibration equations for palmitic (r² = 0.54; RPD = 1.41) and stearic acids (r² = 0.52; RPD = 1.44) was too low for allowing their application in practice. NIRS discrimination of oil content and concentrations of oleic and linoleic acids was mainly based on the spectral region from 2240 to 2380 nm. Practical applications : NIRS is a high‐throughput analytical technique that allows fast measurement of several traits in a single analysis without using chemical reagents. We evaluated the feasibility of analyzing oil content and concentrations of palmitic, stearic, oleic, and linoleic acids in almond flour using fruits collected during 2 years from a world germplasm collection. The fruits collected in 2009 were used for NIRS calibration, whereas the fruits collected in 2010 were used for validation. NIRS equations were highly accurate for measuring oil content and concentrations of oleic and linoleic acids, which are important traits defining the quality of almond flour for specific uses in the food industry. These results have applications both in the research laboratory and the food industry, where NIRS is becoming a widely used technique for quality control.     

Improved Estimation of Oil,Linoleic and Oleic Acid and Seed Hull Fractions in Safflower by NIRS

Near-infrared reflectance spectroscopy (NIRS) of intact seeds allows the non-destructive estimation of seed quality parameters which is highly desirable in plant breeding. Together with yield, oil content and quality, a main aim in safflower (Carthamus tinctorius L.) breeding is the selection of genotypes with a low percentage of empty seeds even under cooler climates. We developed NIRS calibrations for seed oil content, oleic and linoleic acid content, the seed hull fraction and the percentage of empty seeds using seed meal and intact seeds. For the different calibrations 108–534 samples from a safflower breeding program with lines adapted to German conditions, were analyzed with reference analyses (Soxhlet, gas chromatography), and scanned by NIRS as intact seeds and seed meal. Calibration equations were developed and tested through cross validation. The coefficient of determination of the calibration (R ²) for intact seeds ranged from 0.91(oil content), 0.90 (seed hull fraction), 0.84 (empty seeds), 0.73 (linoleic acid) to 0.68 (oleic acid). The coefficient of determination of the cross validation was higher for seed meal than for intact seeds except for the parameter seed hull fraction. The results show that NIRS calibrations are applicable in safflower breeding programs for a fast screening.     

混合脂肪酸的分离

以一般油脂加工副产物十八碳混合脂肪酸为原料,采用配合结晶梯度冷冻反萃取分离技术,不经任何热处理以避免聚合作用的发生,使混合脂肪酸中的饱和脂肪酸与不饱和脂肪酸分离,同时将不饱和脂肪酸分成油酸和(亚油酸+亚麻酸)两组分。后者含量可达95%以上。     

Geometrical isomerization of polyunsaturated fatty acids in physically refined rapeseed oil during plant‐scale deodorization

The effect of the operating temperature (between 220 and 270 °C) on the formation of trans isomers of linoleic and linolenic acids in physically refined rapeseed oil during deodorization in a plant‐scale semicontinuous tray‐type deodorizer (capacity 10 t/h) was investigated. The industrial procedures of physical refining consisted of a two‐step bleaching and deodorization process. The degree of isomerization of linoleic acid ranged from 0.33 to 4.77% and that of linolenic acid from 4.43 to 45.22% between 220 and 270 °C, respectively. A relation between the logarithm of the degree of isomerization and the deodorization temperature can be approximated by statistically highly significant linear functions for both linoleic and linolenic acids. Oleic acid was resistant to the heat‐induced geometrical isomerization. The values found for the ratio between the degrees of isomerization of linolenic and linoleic acids, slightly decreasing with increasing temperature, were equal to 13.6 and 12.9 at 230 and 240 °C, respectively. Two trans isomers of linoleic acid, exclusively with one double bond isomerized into trans configuration, and four trans isomers of linolenic acid, mostly with one double bond isomerized into trans configuration, were determined in deodorized rapeseed oils. Linolenic acid was observed to be the main source responsible for the formation of nearly all trans fatty acids in physically refined rapeseed oil. At 235 °C, a deodorization temperature considered as a reasonable technological compromise, the content of trans fatty acids in plant‐scale physically refined rapeseed oil was less than 1% of total fatty acids, which would be acceptable for further application.     

Comparative studies on composition of cardiac phospholipids in rats fed different vegetable oils

Male Sprague-Dawley rats were fed diets for 1 or 16 weeks, containing 20% by weight vegetable oils differing widely in their oleic, linoleic and linolenic acid content. No significant changes were observed in the level of the cardiac lipid classes. The fatty acid composition of the 2 major phospholipids, phosphatidylcholine and phosphatidylethanolamine, showed a remarkable similarity between diets in the concentration of total saturated, C22 polyunsaturated and arachidonic acids. Monounsaturated acids were incorporated depending on their dietary concentration, but the increases were moderate. Dietary linolenic acid rapidly substituted C22 polyunsaturated fatty acids of the linoleic acid family (n−6) with those from the linolenic acid family (n−3). The results suggest that dietary linolenic acid of less than 15% does not inhibit the conversion of linoleic to arachidonic acid but the subsequent conversion of arachidonic acid to the C22 polyunsaturates was greatly reduced. Significant amounts of dietary monounsaturated fatty acids were incorporated into cardiac cardiolipin accompanied by increases in polyunsaturated fatty acids, apparently to maintain an average of 2 double bonds/molecule. The cardiac sphingomyelins also accumulated monounsaturated fatty acids depending on the dietary concentration. It is quite evident from the results of this study that the incorporation of oleic acid and the substitution of linolenic for linoleic acid-derived C22 polyunsaturated fatty acids into cardiac phospholipids was related to the dietary concentration of these fatty acids and was not peculiar to any specific oil. Even though it is impossible to estimate the effect of such changes in cardiac phospholipids on membrane structure and function, results are discussed which suggest that the resultant membrane in the Sprague-Dawley male rat is more fragile, leading to greater cellular breakdown and focal necrosis. Contribution No. 914 from the Animal Research Institute.     

越南安息香种子脂肪酸的在线甲基化-GC分析研究

建立了分析越南安息香种子油、果实和果壳的脂肪酸组成的在线甲基化-气相色谱法。将微克级的安息香样品与2μL衍生化试剂三甲基氢氧化硫（0.2 mol/L）加入裂解器,在350℃下瞬间反应,由气相色谱在线检测到8种脂肪酸甲酯成分,主要有棕榈酸（ C16∶0）、硬脂酸（ C18∶0）、油酸（ C18∶1）、亚油酸（ C18∶2）和亚麻酸（ C18∶3）,不饱和脂肪酸含量在84.5%以上,其中亚油酸含量最高,达47.29%。5次平行测定的相对标准偏差（ RSD）小于3.81%。并结合相似性分析法比较了4种不同产地的安息香种仁与6种食用油的脂肪酸组成,相似性结果表明不同产地的安息香种仁的脂肪酸组成相似,其脂肪酸组成与食用植物油相近,与玉米油的组成分布最为接近,相似系数在0.987~0.990,且越南安息香种子中人体必需的多不饱和脂肪酸含量（ C18∶2和C18∶3）与大豆油和葵花籽油相近,高于一般植物油,具有较高的营养价值。结果表明该法简便、快速、准确,适合越南安息香种子油脂的测定。     

Fatty acid composition of oleaster pulp and pit oils

Fatty acid compositions of oleaster pulp and pit oils were determined by gas chromatography in 4 samples of different varieties. Pit oils were highly unsaturated, containing >90% linoleic, oleic, and linolenic acids, as well as traces of palmitoleic acid. Saturated fatty acids consisted of palmitic and stearic acids with traces of arachidic acid. Pulp oils showed fatty acid compositions entirely different from that of pit oils. They contained 9 saturated fatty acids, C₁₂ to C₂₄, some of them with high quantities, up to 34.9%, of the total fatty acids. Unsaturated fatty acids, mainly oleic and linoleic, with low quantities of palmitoleic and linolenic acids composed about one-third of the total fatty acids.     

Fatty acid composition of oil from soybean leaves grown at extreme temperatures

Leaves from soybean (Glycine max (L.) Merr.) plants were assayed to determine if the relationship between temperature and relative fatty acid composition observed in the seed oil also existed for the triglycerides in the leaf oil. Leaf samples were harvested from eight soybean lines (A5, A6, C1640, Century, Maple Arrow, N78-2245, PI 123440 and PI 361088B) grown at 40/30,28/22 and 15/ 12°C day/night. At 40/30 and 28/22°C, seven fatty acids were observed at a level greater than 1.0%. These included the five major fatty acids found in the seed oil: palmitic (16:0), stearic (18:0), oleic (18:1), linoleic (18:2) and linolenic (18:3) acid; plus two fatty acids that had retention times the same as palmitoleic (16:1) and γ-linolenic (18:3 g) acid. In addition, an eighth fatty acid that had a retention time the same as behenic (22:0) acid was found in the leaves of all lines at 15/12°C. Palmitic, palmitoleic and stearic acid content did not differ significantly over temperatures. The oleic and linoleic acid content were each highest at 15/12°C, while the γ-linolenic and the linolenic acid content were each highest at 40/30°C. The fatty acid composition of the triglyceride portion of the leaf oil did not display the same pattern over temperatures as that observed for seed oil.     

Determination of the Fatty Acid Composition in Tree Peony Seeds Using Near-Infrared Spectroscopy

Tree peonies (Paeonia Sect Moutan DC) are an emerging oil crop because of their high oil and α‐linolenic acid (ALA) content. This research was to investigate the potential use of near infrared reflectance spectroscopy (NIRS) for estimating the major fatty acids contents, such as palmitic acid (C16:0), oleic acid (C18:1), linoleic acid (C18:2) and linolenic acid (C18:3) in tree peonies. A total of 115 small seed samples and 447 single seeds were selected to calibrate the predictive models. NIRS absorbance spectra were collected using a Fourier transform near infrared (FT‐NIR) spectrometer for the small seed samples, and acousto‐optic tunable filter‐near infrared (AOTF‐NIR) for the single seed samples. Statistical analysis was performed with partial least squares (PLS). For the husked samples, C18:3, C18:1 and C18:2 showed the highest correlation coefficient of validation (R_v; = 0.9756, 0.9467 and 0.8485, respectively) and the ratio of performance to deviation (RPD; = 3.58, 1.91 and 2.17, respectively); however, C16:0 did not reach expectations (R_v = 0.7783, RPD = 1.32). For intact samples, C18:3 showed the best prediction (R_v = 0.9096, RPD = 3.14), followed by C18:2 (R_v = 0.8479, RPD = 1.96). The results for C18:1 were poor (R_v = 0.7237, RPD = 1.70). For single seeds, only the results for C18:3 (R = 0.9150, RPD = 1.73) were good in the husked seed samples. It was concluded that NIRS can be used to rapidly assess the content of the major fatty acids in small samples.     

Measurement of Whole Soybean Fatty Acids by Near Infrared Spectroscopy

Whole soybean fatty acid contents were measured by near infrared spectroscopy. Three calibration algorithms—partial least squares (PLS), artificial neural networks (ANN), and least squares support vector machines (LS-SVM)—were implemented. Three different validation strategies using independent sets and part of calibration samples as validation sets were created. There was a significant improvement of the prediction precision of all fatty acids measured on relative concentration of oil compared with previous literature using PLS (standard error of prediction of 0.85, 0.42, 1.64, 1.67, and 0.90% for palmitic, stearic, oleic, linoleic and linolenic acids respectively). ANN and LS-SVM methods performed significantly better than PLS for palmitic, oleic and linolenic acids. Calibration models developed on relative concentrations (% of oil) were compared to prediction models created on absolute fatty acid concentration (% of weight) and corrected to relative concentration by multiplying by the predicted oil content. While models were easier to develop in absolute concentration (higher coefficients of determination), the multiplication of errors with the total oil content model resulted in no net precision improvement.     

Determination of the fatty acid profile by 1H‐NMR spectroscopy

The common unsaturated fatty acids present in many vegetable oils (oleic, linoleic and linolenic acids) can be quantitated by ¹H‐nuclear magnetic resonance spectroscopy (¹H‐NMR). A key feature is that the signals of the terminal methyl group of linolenic acid are shifted downfield from the corresponding signals in the other fatty acids, permitting their separate integration and quantitation of linolenic acid. Then, using the integration values of the signals of the allylic and bis‐allylic protons, oleic and linoleic acids can be quantitated. The procedure was verified for mixtures of triacylglycerols (vegetable oils) and methyl esters of oleic, linoleic and linolenic acids as well as palmitic and stearic acids. Generally, the NMR (400 MHz) results were in good agreement with gas chromatographic (GC) analyses. As the present ¹H‐NMR‐based procedure can be applied to neat vegetable oils, the preparation of derivatives for GC would be unnecessary. The present method is extended to quantitating saturated (palmitic and stearic) acids, although in this case the results deviate more strongly from actual values and GC analyses. Alternatives to the iodine value (allylic position equivalents and bis‐allylic position equivalents) can be derived directly from the integration values of the allylic and bis‐allylic protons.     

Estimation of Oil Content and Fatty Acid Composition in Cottonseed Kernel Powder Using Near Infrared Reflectance Spectroscopy

Oil content and fatty acid composition in 444 ground cottonseed kernel samples were analyzed using near infrared reflectance spectroscopy (NIRS). Calibration equations were developed for oil and fatty acid contents with the modified partial least squares (MPLS) regression method. The correlations between NIRS and reference values in external validation were in agreement with the predictions in calibration. Each equation was assessed based on the relative prediction determinant for external validation (RPD_v). Equations corresponding to total oil content (RPD_v = 11.495) and linoleic acid (RPD_v = 5.026) showed high accuracy. For palmitic acid (RPD_v = 1.914), myristic acid (RPD_v = 1.724) and oleic acid (RPD_v = 1.999), the equations were predicted with relatively high accuracy while those for palmitoleic acid (RPD_v = 0.686), stearic acid (RPD_v = 0.792), linolenic acid (RPD_v = 0.475) and 1-eicosenoic acid (RPD_v = 0.619) were poorly predicted. The equations for traits with RPD_v > 1.5 could be reliably used in screening samples for breeding programs.     

Quantification and Compositional Diversity of Fatty Acid Methyl Esters Profile in Nigella sativa L. Germplasm

Nigella sativa L. is an annual underutilized crop of enormous significance, it contains more than 100 bioactive constituents having both pharmaceutical and industrial applications. Nigella sativa L. germplasm consisting of 32 genotypes was quantified for palmitic acid, stearic acid, oleic acid, linoleic and linolenic acid and results obtained varied in percentage. Lipid extracted by chloroform methanol 2:1 (24–37 %) was higher compared to n-hexane (18–35 %) and chloroform methanol 1:3 (18–34 %). Extraction with solvent chloroform methanol 2:1 yielded a higher quantity of oil contents, hence recommended. The polyunsaturated fatty acids were higher than monounsaturated fatty acids. Stearic and palmitic acids were positively correlated as were stearic and linoleic acids. It is inferred that breeding for increased stearic acid, linolenic acid and reduced palmitic acid can be achieved through modern breeding methods. The genotypes rich in oil and oleic-linoleic acid, viz., Pk-020545, Pk-020576, Pk-020609, Pk-020620, Pk-020654, Pk-020699, Pk-020720, Pk-020780, Pk-020874 and Pk-020878, have been suggested for crop improvement programs and could augment the supply of edible oil as well as a biofuel substitute with large scale cultivation.     

Betula platyphylla var.japonica Seed Oil: A rich source of linoleic acid

Component fatty acids of the oil extracted fromBetula platypbylla Sukatchev var.japonica Hara (Betulaceae) seeds were analyzed by gas liquid chromatography. The predominant fatty acid was linoleic acid (87%), and together with oleic and linolenic acids the 18-carbon unsaturated acids amounted to 97% of the total acids.     

Varietal difference in lipid content and fatty acid composition of highbush blueberries

Lipids from five cultivars of highbush blueberries (Vaccinium corymbosum L.) were extracted and fractionated into neutral lipids (60–66%), glycolipids (20–22%) and phospholipids (14–18%). The major fatty acids in all fractions were palmitic (16∶0), oleic (18∶1), linoleic (18∶2), and linolenic (18∶3) acids. All lipid classes had a large concentration of C₁₈ polyunsaturated acids (84–92%), indicating that blueberries are a rich source of linoleic and linolenic acids. Changes in the fatty acid composition of neutral lipids and phospholipids were not significantly different among the five cultivars, but significant differences were noted in the ratios of linoleic and linolenic acids in the glycolipids fraction.     

trans-Polyunsaturated fatty acids in French edible rapeseed and soybean oils

The fatty acid compositions of rapeseed and soybean oils marketed in France have been determined by gas liquid chromatography on a fused-silica capillary column coated with a 100% cyanopropyl polysiloxane stationary phase. Under the operating conditions employed, methyl esters of linolenic acid geometrical isomers could be separated and quantitated easily without any other complementary technique. With only one exception, all samples under study (eight salad oils and five food samples) contain geometrical isomers of linolenic acid in measurable, although variable, amounts. Totaltrans-18:3 acids may account for up to 3% of total fatty acids. This value corresponds to a degree of isomerization (percentage oftrans isomers relative to total octadecatrienoic acids) of 30%. Examination of our data indicates that the distribution pattern of linolenic acid geometrical isomers does not depend on the degree of isomerization. The two main isomers always have thec,c,t and thet,c,c configurations. These isomers occur in the almost invariable relative proportions of 47.8±1.7% and 41.1±1.0%, respectively. The third mono-trans isomer is present in lower amounts−6.5±0.7%. The only di-trans isomer that can be quantitated with sufficient accuracy is thet,c,t isomer (4.9±1.5%). Mono-trans isomers of linoleic acid are also present in these oils. However, their maximum percentages are lower than those determined for linolenic acid geometrical isomers. In the oils showing the highest degrees of isomerization,trans isomers of linoleic acid account for 0.5% (rapeseed oils) and 1% (soybean oils) of total fatty acids. Taking into account all data, it would appear that the probability of isomerization of linolenic acid is about 13–14 times that of linoleic acid.