The use of high performance liquid chromatography for the quality survey of frying fats and oils

Summary During the process of deep fat frying the frying fat or oil undergoes complex chemical reactions which lead to its deterioration. For the quality survey of frying fats or oils the time-consuming determination of total polar components by column chromatography is an approved standard method. High performance liquid chromatography (HPLC) can be used to substitute this technique. Moreover, HPLC proved to be a useful tool for the determination of the qualitative and quantitative composition of fatty acid and polar substances which change during the frying process. Presented at the 21^st ISC held in Stuttgart, Germany, 15^th–20^th September, 1996     

Carbonyl value in monitoring of the quality of used frying oils

In this study, a set of frying oil samples of different compositional properties but passed qualitative and quantitative standards, which were of various vegetable oil sources (individually or as blends), were obtained from seven of big oil factories in Iran. Before starting the frying process, all the frying oils had carbonyl values (CV) higher than 2 micromol g(-1). The CV of most frying oils linearly increased until the end of the frying process, whereas for some of them, the CV increased and reached a maximum and then decreased to some extent. However, in a set of frying oil samples on average, the CV linearly increased as the frying time increased. There was a linear relationship between the CV and total polar compounds (TPC) throughout the frying process with a high determination coefficient (R(2)=0.9747). The values found for carbonyl compounds of the frying oils during frying process ranged from 7.76+/-0.00 to 123.45+/-3.70 micromol g(-1). Assuming that the limit of acceptance for TPC is 24%, this was roughly corresponded to 43.50 micromol g(-1) for CV.     

Fast GC for the analysis of fats and oils

Fast and conventional GC techniques were both applied to ten different lipidic matrices and the results then compared. The fats and oils were of fish, animal, and vegetable origin and were all simultaneously transesterified with acidic methanol before performing batch analysis of the fatty acid methyl esters (FAMEs) obtained. All FAMEs samples were consecutively analyzed three times by each method. The fast method significantly reduced the time required for analysis by a factor of 5 while maintaining a similar resolution. Furthermore, the reproducibility of relative quantitative data was measured on going from one method to the other. Peak identification was achieved through conventional GC‐MS in combination with linear retention index values contained in a home library and information derived from comprehensive 2D GC group patterns.     

Monitoring the quality of frying oils using a nanolayer coated optical fiber refractometer

The analysis of the quality of food oils is of paramount importance, because the degradation of oils can lead to formation of harmful substances to the human organism. With the increase of the degradation of oils an increase of its refractive index occurs. The objective of this work is to develop and to characterize optical fiber refractometers sensitive to variations of refractive index of food oil samples. The optical fiber refractometers thanks to the intrinsic characteristics make them suitable for monitoring the quality of frying oils. They possess the advantages to require small volumes of sample for analysis, do not contaminate the sample, and supply the response in real time. In this work a long period grating (LPG) as refractometer is used because of their sensitivity to refractive index of the external media: degraded and not degraded frying oil samples. The oil samples had been characterized by the analysis of total polar components. The refractive index of oil is above 1.47, this region the LPG does not show enough sensitivity, a nanolayer of an organic material was coated onto the fiber. Using the Langmuir-Blodgett technique the response of LPG is modified according to the refractive index and thickness of the film. The deposition of the film modifies the rates effective modes of cladding, thus improving the response of the changes in the refractive index of the external media higher than that the refractive index of the cladding (n = 1.457).     

Determination of higher carbonyl compounds in used frying fats by HPLC of DNPH derivatives

In current analytical practice, simple methods are required for assessing the quality of a deep-frying fat after some time of use. Therefore, a new procedure was developed for the fast and selective determination of higher carbonyl compounds, i.e., those triglycerides resulting from the oxidation and/or oxidative cleavage of double bonds in unsaturated fatty acids. For analysis, a fat sample is dissolved in a 1-butanol/toluene mixture containing 6-undecanone as an internal standard. Aldehydes and ketones present are allowed to react with 2,4-dinitrophenylhydrazine (DNPH) in acidic solution for at least 1 h at room temperature. The mixture is injected directly onto a reversed phase HPLC column that is eluted with a very steep gradient between methanol and tert-butylmethyl ether (TBME) and is fitted with a UV detector set at 370 nm. In this way, the DNPH derivatives of all higher carbonyl compounds are eluted as one single peak. The result is calculated as milliequivalents of carbonyls per kg of fat (meq kg(-1)). The method takes a minimum of time and reagents and only requires the usual equipment.     

Polycyclic aromatic hydrocarbons in edible fats and oils: occurrence and analytical methods

This review deals with analytical methods for polycyclic aromatic hydrocarbon (PAH) determination in oils and fats. The data reported in the introduction deal with PAH dietary intake from this group of food and contamination levels recently found by some authors in different vegetable oils, stressing the importance of establishing a method suitable for routine analyses. Traditional sample preparation relies on tedious, time-consuming procedures. They generally consist of an extraction step (liquid-liquid partition, caffeine complexation, saponification) followed by one or more purification procedures (column chromatography, thin-layer chromatography, solid-phase extraction). The analytical determination is usually carried out by HPLC and spectrofluorometric detection, or through high-resolution capillary GC coupled to flame ionisation detection or mass spectrometry. LC is a valid alternative to the traditional sample preparation, and off-line LC-LC allows performing an accurate PAH analysis in less than 2 h. Also supercritical fluid extraction, allowing performing both extraction and clean-up in one combined step, is a promising technique. Hyphenated techniques such as LC-GC and LC-LC-GC seem to be very promising. A completely on-line method for alkylated PAH determination in oils or lipidic extracts contaminated with mineral oil involves a two-dimensional LC-step with intermediate eluent evaporation and GC transfer through a vaporiser/overflow interface.     

Lorentz-Lorenz expression as a new analytical constant for fats (ghee) and oils

Zusammenfassung Der Farbstoff Fast Grey R.A. hat sich als empfindliches Reagens für die colorimetrische Mikrobestimmung von Zirkonium erwiesen. Man kann Zr-Konzentrationen zwischen 0,02 und 8 ppm bei einer Wellenlänge von 570 m bestimmen. Störend wirken u. a. die Kationen Cu²⁺, Ni²⁺ und Fe³⁺. Ascorbinsäure beseitigt jedoch die störende Wirkung nicht zu großer Mengen Eisen. U, Co, Al, Th, Bi, Zn, die Alkalien und die Seltenen Erden stören nicht.     

Determination of silicon in fats and oils by electrothermal atomic absorption spectrometry with in-furnace air oxidation

A graphite-furnace atomic absorption spectrometric emthod is reported for determination of dimethylpolysiloxane (silicone) in edible fats and oils. It incorporates an air-oxidation step in the furnace program to reduce matrix interferences. The detection limit is 0.3 mg kg^?1 in soils, and short-term precision is about 6% at silicon concentrations of 1.7–2.0 mg kg^?1. The procedure was successfully applied to a variety of commercial frying fats and oils, to quantify silicone loss during polish filtration during oil manufacture, to quantify sorption of antifoam onto fried food, and to detect fugitive sources of silicone encountered in deep-fat frying operations.     

New opportunity for enzymatic modification of fats and oils with industrial potentials

Novozym 435 (Candida antarctica lipase)-catalyzed glycerolysis of commercial oils and fats to produce monoglycerides (MGs) was investigated using a tetraammonium-based ionic liquid (IL) as a reaction medium. A 90% yield of MGs and nearly 100% conversion of triglycerides in this ionic liquid were achieved, markedly higher than in normal solvents. The amphiphilic structure of cocosalkyl pentaethoxi methyl ammonium methosulfate (CPMA.MS) was suggested to be capable of creating a compatible system for glycerol, oils and fats, as well as inducing the shift of reaction equilibrium to the formation of MG. Interestingly, over a wide range of solvent dosage, the higher yields of MG were observed, indicating the good bulky substrate-tolerating capacity of the IL. The universal validity of the protocol was verified by being successfully applied to different commercial oils and fats. Excellent operational stability of the lipase and the reusability of IL were also observed in consecutive batchwise reactions. The results indicate that the protocol developed in this work provides a new environmentally benign "solution" to the enzymatic modification of fats and oils with industrial potentials.     

Determination of specific heats of some edible oils and fats by differential scanning calorimetry

Measurements of specific heat as a function of temperature were carried out with a differential scanning calorimeter on rape-seed, soybean, sunflower and corn oils and on lard.

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Zusammenfassung Es wurden Messungen der spezifischen Wärme als Funktion der Temperatur von Raps-, Soia-, Sommerblumen- und Mais-ölen und von Schmalz mit Hilfe von einem Dynamische-Differenz-Kalorimeter durchgeführt.

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微波消化-石墨炉原子吸收法测定食用油脂中的铜

用微波消化技术对各种食用油脂试样进行预处理，针对样品特性，优化较佳的微波消化条件与操作参数，建立了用微波消化－石墨炉原子吸收法测定食用油脂中的铜，减少了样品处理过程中的损失，回收率为92.4%-96.2%；RSD为3.0%-3.6%, 检出限为0.05mg/kg。     

Determination of total <Emphasis Type="Italic">trans</Emphasis> fats and oils by infrared spectroscopy for regulatory compliance

The mandatory requirement in many countries to declare the amount of trans fat present in food products and dietary supplements has led to a need for sensitive and accurate methodologies for the rapid quantitation of total trans fats and oils. Capillary gas chromatography (GC) and infrared spectroscopy (IR) are the two methods most commonly used to identify and quantify trans fatty acids for food labeling purposes (see the article by Delmonte and Rader in this ABC issue for a detailed presentation of GC methodology). The present article provides a comprehensive review of the IR technique and the current attenuated total reflection (ATR) Fourier-transform (FT) IR methodologies for the rapid determination of total trans fats and oils. This review also addresses potential sources of interferences and inaccuracies in FTIR determinations, particularly those done at low trans levels. Recent observations have shown that the presence of saturated fats caused interferences in the FTIR spectra observed for trans triacylglycerols. The recognition and resolution of previously unresolved quantitative issues improved the accuracy and sensitivity of the FTIR methodology. Once validated, it is anticipated that the new negative second-derivative ATR-FTIR procedure will make IR spectroscopy more suitable than ever, and a rapid alternative and/or complementary method to GC, for the rapid determination of total trans fats for regulatory compliance. Figure Infrared light bouncing inside an internal reflection crystal     

GC/MS combined with chemometrics methods for quality control of Schizonepeta tenuifolia Briq: Determination of essential oils

A simple and rapid gas chromatography/mass spectrometry (GC/MS) analysis method was developed for the determination of essential oils in the crude extract of Schizonepeta tenuifolia Briq (Sch.t.Briq). Five major volatiles (menthone, pulegone, 2-hydroxy-2-isopropenyl-5-methylcylohexanone, cis-pulegone oxide, and schizonal) were extracted and isolated from Sch.t.Briq as marker compounds for use in the quality control of herbal medicines. Various extraction techniques, such as solvent immersion, mechanical shaking, and sonication, were evaluated, and the greatest efficiency was observed with sonication extraction using petroleum ether. The dynamic range of the GC/MS method depended on the specific analyte; acceptable quantification was obtained between 10 and 1000 μg/mL for menthone and pulegone, and between 2.5 and 75.0 μg/mL for 2-hydroxy-2-isopropenyl-5-methylcylohexanone, cis-pulegone oxide, and schizonal. The method was deemed satisfactory by inter- and intra-day validation and exhibited both high accuracy and precision, with a relative standard deviation < 10%. Overall limits of detection were approximately 0.40–0.50 μg/mL, with a standard deviation (σ)-to-calibration slope (s) ratio (σ/s) of 3. The limit of quantitation in our experiments was approximately 2.5 μg/mL at a σ/s of 10. On the basement of method validation, 21 samples of Sch.t.Briq collected from markets in Korea were monitored for the quality control. In addition, principal component analysis (PCA) and hierarchical cluster analysis (HCA) were performed on the analytical data of 21 different Sch.t.Briq samples in order to classify samples that were collected from different regions.     

Colorimetric determination of lipid hydroperoxides in oils and fats with microperoxidase

The use of the peroxidase-like activity of microperoxidase for the calorimetric determination of lipid hydroperoxides in oils and fats has been investigated. The principle of the determination is that 4-aminoantipyrine and N,N-diethylaniline are coupled oxidatively by the hydroperoxides through the action of microperoxidase, yielding a violet colour with maximum absorbance at 554 nm. The response of the microperoxidase system is enhanced by the presence of acetonitrile. The method has been successfully applied to the determination of methyl linoleate hydroperoxide, tert-butyl hydroperoxide and the hydroperoxides in oil and fat samples (soybean oil, linseed oil, olive oil, salad oil, butter and lard). The results agreed closely with those obtained by the iodometric method. The proposed method permitted the determination of the hydroperoxides at 0.5-0.05 mumole levels, with the same sensitivity regardless of sample type tested, with satisfactory reproducibility compared with that obtained by the conventional assay methods.     

Lipophilicity of oils and fats estimated by TLC

A representative series of natural toxins belonging to alkaloids and mycotoxins classes was investigated by TLC on classical chemically bonded plates and also on oils‐ and fats‐impregnated plates. Their lipophilicity indices are employed in the characterization and comparison of oils and fats. The retention results allowed an accurate indirect estimation of oils and fats lipophilicity. The investigated fats and oils near classical chemically bonded phases are classified and compared by means of multivariate exploratory techniques, such as cluster analysis, principal component analysis, or fuzzy‐principal component analysis. Additionally, a concrete hierarchy of oils and fats derived from the observed lipophilic character is suggested. Human fat seems to be very similar to animal fats, but also possess RP‐18, RP‐18W, and RP‐8.     

Utilizing biotechnology in producing fats and oils with various nutritional properties

The role of dietary fat in health and wellness continues to evolve. In today's environment, trans fatty acids and obesity are issues that are impacted by dietary fat. In response to new information in these areas, changes in the amount and composition of edible fats and oils have occurred and are occurring. These compositional changes include variation in fatty acid composition and innovation in fat structure. Soybean, canola, and sunflower are examples of oilseeds with varied fatty acid composition, including mid-oleic, high-oleic, and low-linolenic traits. These trait-enhanced oils are aimed to displace partially hydrogenated vegetable oils primarily in frying applications. Examples of oils with innovation in fat structure include enzyme interesterified (EIE) fats and oils and diacylglycerol oil. EIE fats are a commercial edible fat innovation, where a lipase is used to modify the fat structure of a blend of hard fat and liquid oil. EIE fats are aimed to displace partially hydrogenated vegetable oils in baking and spread applications. Diacylglycerol and medium-chain triglyceride (MCT)-based oils are commercial edible oil innovations. Diacylglycerol and MCT-based oils are aimed for individuals looking to store less of these fats as body fat when they are used in place of traditional cooking and salad oils.