A new Fourier transform infrared method for the determination of moisture in edible oils

A rapid, practical, and accurate Fourier transform infrared (FT-IR) method for the determination of moisture content in edible oils has been developed based on the extraction of water from oil samples into dry acetonitrile. A calibration curve covering a moisture content range of 0-2000 ppm was developed by recording the mid-infrared (MIR) spectra of moisture standards, prepared by gravimetric addition of water to acetonitrile that had been dried over molecular sieves, in a 500 microm ZnSe transmission flow cell and ratioing these spectra against that of the dry acetonitrile. Water was measured in the resulting differential spectra using either the OH stretching (3629 cm(-1) or bending (1631 cm(-1)) bands to produce linear standard curves having standard deviations (SDs) of approximately +/-20 ppm. For moisture analysis in oils, the oil sample was mixed with dry acetonitrile in a 1:1 w/v ratio, and after centrifugation to separate the phases, the spectrum of the upper acetonitrile layer was collected and ratioed against the spectrum of the dry acetonitrile used for extraction. The method was validated by standard addition experiments with samples of various oil types, as well as with oil samples deliberately contaminated with alcohols, hydroperoxides, and free fatty acids to investigate possible interferences from minor constituents that may be present in oils and are potentially extractable into acetonitrile. The results of these experiments confirmed that the moisture content of edible oils can be assessed with high accuracy (on the order of +/-10 ppm) by this method, thus providing an alternative to the conventional, but problematic, Karl Fischer method and facilitating the routine analysis of edible oils for moisture content.     

Production and characterization of pyrolytic oils by pyrolysis of waste machinery oil

The main objective of this work is to propose an alternative method for evaluation of the waste machinery oil which is an environmental problem in Turkey. For this purpose, pyrolysis of waste machinery oil was conducted in a tubular reactor. Effect of the experimental conditions (various temperatures, catalyst type) on the formation of pyrolytic oil, gas, and char was investigated. Nickel supported on silica and zeolite (HZSM-5) were used as catalysts. Properties of the pyrolytic oils were characterized by gas chromatograph equipped with a mass selective detector (GC–MS), gas chromatography with flame ionization detector (GC–FID for boiling point range distribution), nuclear magnetic resonance (¹H NMR) spectroscopy, higher heating value measurement, and elemental analysis. The behavior of the metals in the waste machinery oil and the pyrolytic oil samples was also quantitatively detected by inductively coupled plasma (ICP) analysis. As, Cd and Cr contents of the all pyrolytic oils were found as <0.05 ppm, while Cu content of the pyrolytic oils varied between 0.3 ppm and 0.61 ppm. Only Vanadium contents of the pyrolytic oils obtained at 800 °C (0.342 ppm) and in the presence of HZSM5 (0.57 ppm) increased compared to that obtained by waste machinery oil (0.1 ppm). Lower metal contents of the pyrolytic oils reveal that pyrolysis of the waste machinery oils leads to the formation of environmental friendly pyrolytic oils with higher heating values.     

Influence of fatty acids in waste cooking oil for cleaner biodiesel

Physiochemical properties of biodiesel, a sustainable and green alternative fuel produced from renewable resources, are greatly influenced by the structural features of polyunsaturated, monounsaturated and saturated fatty acids. Two feedstock oils, potentially contribution to cleaner technologies, refined cooking oil and waste cooking oil derived from palm olein have been studied. Fatty acid compositions of the refined cooking oil and waste cooking oil were analysed and confronted with other literature sources. Critical parameters such as cetane number (CN), iodine value, cold filter plugging point (CFPP) and oxidation stability (OS) were correlated with long-chain saturated factor and degree of unsaturation (DU) of fatty acid to match the international standards of cleaner biodiesel. OS in biodiesel has been met with the absence of linolenic acid. High saturated fatty acid provides high CN. The iodine value of feedstock oil met the European standard where the DU of the oils was less than 138. However, CFPP of refined cooking oil and waste cooking oil did not meet the demanding Spanish regional (RD 61/2006) standard due to the presence of stearic and palmitic acid, which tended to clog the fuel filter by precipitating while the biodiesel becomes cool. With the proposed triangular chart for biodiesel properties prediction, potential biodiesel fuels from various feedstock oils can be analysed.     

Antioxidant coating of micronsize droplets for prevention of lipid peroxidation in oil-in-water emulsion

Fast lipid peroxidation in emulsified oils results in carcinogens formation and product rancidity. Prevention of oxidative degradation in oil-in-water emulsion has been achieved by encapsulating of each droplet of dispersed phase in antioxidant multilayer coating shell. The fabrication comprised placing a surface-active ionic emulsifier at the oil/water interface followed by stepwise alternate adsorption a biocompatible polyelectrolyte and antioxidant layers. Uncoupled polyelectrolyte macromolecules and antioxidant were thoroughly removed from formulation, thus the protection was entirely attributed to the droplets' shell. The experiments were performed using linseed oil, the richest source of highly unstable omega-3 alpha linolenic essential fatty acid. Bovine serum albumin (BSA) was exploited as an anionic emulsifier. The biodegradable coating shell was formed of poly-l-arginine (PARG) and dextran sulfate (DS) applied as a polycation and a polyanion respectively. Tannic acid (TA) known as a natural antioxidant and possessing antimicrobial properties was used as a protective remedy. Oil microdroplets coated with TA-containing shell displayed physical-chemical and mechanical stability in aqueous phase and over freeze-drying process as determined by ζ-potential measurements, dynamic light scattering (DLS), and confocal laser scanning microscopy (CLSM). Oxidation of emulsified oil was monitored by formation of malondialdehyde (MDA) in the samples quantified by Thiobarbituric Acid Reactive Substances (TBARS) assay. Coating shell with an incorporated layer of TA effectively suppressed oxidation in water-dispersed oil droplets and affected iron-catalyzed oxidation over 15 days of incubation at 37 °C in 0.3 mM FeBr2 solution. Antioxidant activity of TA-containing shell assembled around each oil droplet was found to be higher than that of mixed tocopherols (MT) added to linseed oil in concentration of 10000 ppm.     

Penetration enhancing effects of selected natural oils utilized in topical dosage forms

Abstract

Context: Various natural products, including oils, have been utilized as penetration enhancers due to their “safety profiles”. These oils contain fatty acids promoting skin permeability through lipid fluidization within the stratum corneum; and might therefore be able to effectively enhance transdermal drug delivery.

Objective: We investigated possible penetration enhancing properties of selected oils, utilizing flurbiprofen as marker compound in emulgel formulations. The formulations were compared to a liquid paraffin emulgel and a hydrogel to establish any significant penetration enhancing effects.

Methods: Gas chromatographic analysis of the natural oils was performed at ambient temperature to determine the fatty acid composition in each selected natural oils. Franz cell diffusion studies and tape stripping methods were employed to study delivery of the marker into, and through the skin.

Results: The following rank order for the emulgel flux-values was obtained: Hydrogel >>>> olive oil >> liquid paraffin >> coconut oil > grape seed oil >> Avocado oil ≥ Crocodile oil >> Emu oil.

Discussion: Results suggested that oils containing predominantly mono-unsaturated oleic acid, on average increased the flux of the marker to a larger extent than oils containing an almost even mixture of both mono- and poly-unsaturated fatty acids. Oils comprising saturated fatty acids (SFAs) with alkyl chains between C₁₂ and C₁₄, increased the marker flux to a higher extent than oils containing C₁₆–C₁₈ SFAs. Effects observed for branched fatty acids, however, did not vary significantly from effects for unbranched fatty acids with the same carbon chain length.

Conclusion: Natural oils possess penetration enhancing effects.     

水分散性醇酸树脂的研究

采用酯化法熔融聚合制得水分散性醇酸树脂,提高了水分散性醇酸树脂的外观状态和稳定性.酯化反应的终点通过酸值测定来控制,以6mgKOH/g最为适宜.使用不同的脂肪油合成了不同油度的水分散性醇酸树脂,通过涂膜性能测试确定了最佳的脂肪油种类和最佳的油度值.结果表明:由脱水蓖麻油制得的水分散性醇酸树脂的综合性能最好,油度以50%最为合适.     

Raman and near-infrared spectroscopy for quantification of fat composition in a complex food model system

Raman and near-infrared (NIR) spectroscopy have been evaluated for determining fatty acid composition and contents of main constituents in a complex food model system. A model system consisting of 70 different mixtures of protein, water, and oil blends was developed in order to create a rough chemical imitation of typical fish and meat samples, showing variation both in fatty acid composition and in contents of main constituents. The model samples as well as the pure oil mixtures were measured using Raman and NIR techniques. Partial least squares regression was utilized for prediction, and fatty acid features were expressed in terms of the iodine value and as contents of saturated, monounsaturated, and polyunsaturated fatty acids. Raman spectroscopy provided the best results for predicting iodine values of the model samples, giving validated estimation errors accounting for 2.8% of the total iodine value range. Both techniques provided good results for predicting the content of saturated, monounsaturated, and polyunsaturated fatty acids in the model samples, yielding validated estimation errors in the range of 2.4-6.1% of the total range of fatty acid content. Prediction results for determining fatty acid features of the pure oil mixtures were similar for the two techniques. NIR was clearly the best technique for modeling content of main constituents in the model samples.     

Characterization of vegetable oils by electrospray ionization mass spectrometry fingerprinting: classification, quality, adulteration, and aging

An improved approach for the direct infusion electrospray ionization mass spectrometry (ESI-MS) analysis of vegetable oils is described. The more polar components of the oils, including the fatty acids, are simply extracted with methanol/water (1:1) solution and analyzed by direct infusion ESI-MS in both the negative and positive ion modes. This fingerprinting analysis was applied to genuine samples of olive, soybean, corn, canola, sunflower, and cottonseed oil, to admixtures of these oils, and samples of aged soybean oil. ESI-MS fingerprints in the positive ion mode of the extracts divide the oils into well-defined groups, as confirmed by principal component analysis, whereas ESI-MS fingerprints in the negative ion mode clearly differentiate olive oil from the five other refined oils. The method is also shown to detect aging and adulteration of vegetable oils.     

Influence of fatty acids content in non-edible oil for biodiesel properties

Physical and chemical properties of biodiesel are influenced by the structural features of fatty acid, such as with saturated, monounsaturated and polyunsaturated fatty acids. In this study, seven non-edible oils have been selected, which include waste cooking oil derived palm olein, Calophyllum inophyllum, jatropha oil, castor oil, rubber seed oil, kapok seed oil and karanja oil. The critical parameters, e.g. cetane number (CN), iodine value (IV) and oxidation stability (OS) of biodiesel were correlated with the degree of unsaturated (DU) fatty acid, whereas the cold filter plugging point (CFPP) was correlated with the long chain saturated factor (LCSF). To meet the minimum EU requirement of EN 14214 of the critical parameter, the DU value of the CN was ≤133.5, IV ≤123.2 and OS ≤98.9. The LCSF values satisfied the Spanish regional standard—RD 61/2006 in summer (0 °C) at ≤8.4 and winter (?10 °C) at ≤0.1 of the CFPP. Based on the composition of the saturated, monounsaturated and polyunsaturated fatty acids, a triangular chart for the biodiesel property prediction was developed. This can then be used as a reference for non-edible oils.     

Effects of storage temperature and α-tocopherol on oil recovered from sardine mince

Sardine oil released during sardine mince preparation showed good quality with a low hydroperoxide content, excellent color and high content (19.23%) of eicosapentaenoic acid. Recovered sardine oil was stored at two different temperatures (+4 °C and +35 °C) for 28 days with or without the addition of α-tocopherol (50 and 100 ppm). Peroxide values and thiobarbituric acid reactive substances of control sardine oil significantly increased to reach 29.9 meq O₂/kg oil and 46.48 mg MA/kg during storage at +35 °C, but the increase was considerably less (4.36 meq O₂/kg oil and 13.21 mg MA/kg oil respectively) in oil stored at +4 °C. A slight increase (1.5%) in the free fatty acid content was recorded in oil stored at 35 °C. A significant decrease of polyunsaturated fatty acids was recorded after storage, particularly in oil stored at 35 °C, while higher percentages of saturated and monounsaturated fatty acids were observed. Storage at +4 °C combined with addition of α-tocopherol (100 ppm) had a beneficial effect on sardine oil stability.     

Characterization and matching of oil samples using fluorescence spectroscopy and parallel factor analysis

A novel approach for matching oil samples by fluorescence spectroscopy combined with three-way decomposition of spectra is presented. It offers an objective fingerprinting based on the relative composition of polycyclic aromatic compounds (PACs) in oils. The method is complementary to GC-FID for initial screening of oil samples but can also be used for prescreening in the field, onboard ships, using a portable fluorescence spectrometer. Parallel factor analysis (PARAFAC) was applied to fluorescence excitation-emission matrixes (EEMs) of heavy fuel oils (HFOs), light fuel oils, lubricating oils, crude oils, unknown oils, and a sample collected in the spill area two weeks after the Baltic Carrier oil spill (Denmark, 2001). A total of 112 EEMs were decomposed into a five-factor PARAFAC model using excitation wavelengths from 245 to 400 nm and emission wavelengths from 280 to 550 nm. The PARAFAC factors were compared to EEMs of PAC standards with two to five rings, and the comparisons indicate that each of the factors can be related to a mixture of PACs with similar fluorescence characteristics: a mixture of naphthalenes and dibenzothiophenes, fluorenes, phenanthrenes, chrysenes, and five-ring PACs, respectively. Oils were grouped in score plots according to oil type. Except for HFOs and crude oils, the method easily discriminated between the four oil types. Minor overlaps of HFOs and crude oils were observed along all five PARAFAC factors, and the variability of crude oils was large along factor 2 due to a varying content of five-ring PACs. The spill sample was correctly assigned as a HFO with similar PAC pattern as oil from the cargo tank of the Baltic Carrier by comparing the correlation coefficient of scores for the oil spill sample and possible source oils (i.e., oils in the database).     

Determination of water in NIST reference material for mineral oils

The accuracy of the reference concentrations of moisture in electrical insulating oil RM 8506 and lubricating oil RM 8507 (both of mineral type) and specified by the National Institute of Standards and Technology (NIST) as containing 39.7 and 76.8 ppm (w/w) water, respectively, has recently been the subject of debate in this journal. To shed some further light on this controversy, we report in this correspondence results for these oils obtained by two additional methods, one based on specially designed reagents for diaphragm-free Karl Fischer (KF) coulometry and the other based on the concept of stripping at elevated temperature/continuous KF coulometry. A positive interference effect was shown to take place for RM 8506 when the direct coulometric method was used. If the results are corrected for this, the values including six different procedures varied in the range 13.5-15.6 ppm (w/w). For RM 8507, all values were between 42.5 and 47.2 ppm (w/w), which means that the values recommended by NIST for both reference oils using volumetric titration are about twice as high as those obtained with the other techniques. A possible explanation for this discrepancy is presented.     

Determination of the analytical performance of a headspace capillary gas chromatographic technique and karl Fischer coulometric titration by system calibration using oil samples containing known amounts of moisture

Over the past few years, concerns have been raised in the literature about the accuracy of the Karl Fischer (KF) method for assessing moisture in transformer mineral oils. To better understand this issue, the performance of a static headspace capillary gas chromatographic (HS-CGC) technique was compared to that of KF coulometric titration by analyzing moisture in samples containing known amounts of water and various samples obtained from the National Institute of Standards and Technology (NIST). Two modes of adding samples into the KF vessel were used: direct injection and indirect injection via an azeotropic distillation of the moisture with toluene. Under the conditions used for direct injection, the oil matrix was totally dissolved in the anolyte, which allowed the moisture to be titrated in a single-phase solution rather than in a suspension. The results have shown that when HS-CGC and combined azeotropic distillation/KF titration are calibrated with moisture-in-oil standards, a linear relation is observed over 0-60 ppm H(2)O with a correlation coefficient better than 0.9994 (95% confidence), with the regression line crossing through zero. A similar relation can also be observed when calibration is achieved by direct KF addition of standards prepared with octanol-1, but in this case an intercept of 4-5 ppm is noted. The amount of moisture determined by curve interpolation in NIST reference materials by the three calibrated systems ranges from 13.0 to 14.8 ppm for RM 8506 and 42.5 to 46.4 ppm for RM 8507, and in any case, the results were as high as those reported in the literature with volumetric KF titration. However, titration of various dehydrated oil and solvent samples showed that direct KF titration is affected by a small bias when samples contain very little moisture. The source of error after correction for the large sample volume used for the determination (8 mL) is about 6 ppm for Voltesso naphthenic oil and 4 ppm for toluene, revealing a matrix effect on the measurement. Finally, the results revealed that HS-CGC is a good technique for measuring moisture in oil samples and that the use of azeotropic vapors for introducing moisture into the titrator almost completely eliminates the matrix effect observed with the oil components. Direct KF injection could also be used provided the system is calibrated with moisture-in-oil standards prepared in the same matrix which is to be used for the determination.     

Determination of peptides and proteins in fats and oils

A method for the determination of proteins in fats and oils is described. Proteins were sequentially precipitated with acetone and hydrolyzed, and the produced amino acids were fractionated and quantificated. This analysis protocol afforded a method of high sensitivity and specificity which was fully evaluated and validated. The data obtained showed good accuracy and linearity with excellent reproducibility and recovery. When the method was applied to 40 olive oils, all of them contained proteins in the range 10-50 microg/100 g of oil, suggesting that proteins are nonpreviously described minor components of these oils. In addition, the proteins precipitated were almost exclusively composed by one polypeptide of apparent 4600 molecular weight, which was isolated from olive drupes and partially characterized by amino acid analysis. Similar polypeptides were also detected in other seeds, suggesting that they may constitute a new class of polypeptides in plants with oleosin-like characteristics. Furthermore, the method was also applied to different fats and oils, and all the samples analyzed contained proteins, suggesting that natural fats and oils always contain polypeptides and/or proteins as minor components. These results also suggest that some peptides are soluble in lipid matrixes, where they might be playing unknown functions. The developed procedure provides a methodology for the determination of these components.     

Efficiency of methods for Karl Fischer determination of water in oils based on oven evaporation and azeotropic distillation

The efficiency of azeotropic distillation and oven evaporation techniques for trace determination of water in oils has recently been questioned by the National Institute of Standards and Technology (NIST), on the basis of measurements of the residual water found after the extraction step. The results were obtained by volumetric Karl Fischer (KF) titration in a medium containing a large excess of chloroform (> or = 65%), a proposed prerequisite to ensure complete release of water from the oil matrix. In this work, the extent of this residual water was studied by means of a direct zero-current potentiometric technique using a KF medium containing more than 80% chloroform, which is well above the concentration recommended by NIST. A procedure is described that makes it possible to correct the results for dilution errors as well as for chemical interference effects caused by the oil matrix. The corrected values were found to be in the range of 0.6-1.5 ppm, which should be compared with the 12-34 ppm (uncorrected values) reported by NIST for the same oils. From this, it is concluded that the volumetric KF method used by NIST gives results that are much too high.     

A novel optical sensor for the measurement of furfuraldehyde intransformer oil

Measuring the concentration of furfuraldehyde (FFA) within oil samples taken periodically from power transformers is usually carried out as a means of condition monitoring. Normally, laboratory-based techniques such as high performance liquid chromatography are applied for this measurement. We report the construction of a novel optoelectronic sensor for the determination of FFA in transformer oils to concentrations as low as 0.1 ppm. The sensor will form the basis of a compact and portable instrument that can be used by a nonspecialist operator to determine, on-site, the concentration of FFA in oil extracted from the transformer     

Factors Affecting the Efficiency of a Self-Emulsifying Oral Delivery System

Dosage forms containing a self-emulsifying system have shown significant promise in improving the in vitro dissolution rate and oral absorption of lipophilic drugs. In such a system, a surfactant, or a surfactant plus medium chain monoglyceride (co-emulsifier), is added to a lipophilic vehicle (oil) containing dissolved drug. In the present study, surfactants with different hydrophile-lipophile balance (HLB), fatty acid glycerides (co-emulsifiers) with varying fatty acid (C₈-C₁₈) chain length, and lipophilic vehicles (oils) containing different fatty acid (C₈-C₁₈) compositions were evaluated for their effectiveness in producing self-emulsifying systems. nis investigation showed that the HLB of the surfactant, as well as the fatty acid chain length of the monoglyceride have a significant effect on the performance of the self-emulsifying system; a surfactant with an HLB in the range of 10-15 and a monoglyceride of medium chain fatty acid (C₈-C₁₀) were most effective. Also, there are certain critical concentrations of surfactant and monoglyceride necessary for preparing an optimum self-emulsifying oral drug delivery system.     

Combine Effects of Essential Oils and Packaging on Smoked Rainbow Trout Stored 4°C

In this study, the effect of essential oils (thyme and clove) and packaging treatments (vacuum and modified atmosphere) on the storage of hot smoked rainbow trout (Oncorhynchus mykiss) fillets over a period of 120 days at 4°C was investigated. Fillets were subjected to microbiological (total aerobic mesophilic bacteria, psychrotrophic bacteria, lactic acid bacteria, yeast and mould), chemical analyses (pH, thiobarbituric acid reactive substances and total volatile base nitrogen) and quality testing throughout the storage period. Difference in microbiological and chemical changes between samples was found to be significant (p < 0.05) during storage period. Sensory evaluation showed significant differences between the samples, and V2 and M2 samples were assessed as the most acceptable products by the panellists. In conclusion, essential oils treatment to hot smoking had a positive effect on shelf life of rainbow trout, especially clove oil showed more positive effect when compared with thyme oil. Copyright © 2015 John Wiley & Sons, Ltd.     

Rapid identification of long-chain polyunsaturated fatty acids in a marine extract by HPLC-MS using data-dependent acquisition

The collision-induced dissociation (CID) of a range of deprotonated fatty acid standards was studied using linear ion trap mass spectrometry. Neutral losses of 78, 98, and 136 Da were consistently observed for fatty acids with five or more double bonds. Comparison of the MS/MS spectra of docosahexaenoic acid (DHA) and universally (13)C-labeled DHA allowed the molecular formulas for these neutral losses to be determined as C(6)H(6), C(5)H(6)O(2), and C(8)H(8)O(2). Knowledge of fatty acid fragmentation processes was then applied to identify fatty acids from a sea anemone, Aiptasia pulchella, and dinoflagellate symbiont, Symbiodinium sp. extract. Using HPLC-MS, fatty acids were separated and analyzed by tandem mass spectrometry in data-dependent acquisition mode. Neutral loss chromatograms for 78, 98, and 136 Da allowed the identification of long-chain fatty acids with five or more double bonds. On the basis of precursor ion m/z ratios, chain length and degree of unsaturation for these fatty acids were determined. The application of this technique to an Aiptasia sp.-Symbiodinium sp. lipid extract enabled the identification of the unusual, long-chain fatty acids 24:6, 26:6, 26:7, 28:7, and 28:8 during a single 40 min HPLC-MS analysis.     

聚烯烃抗氧剂1076和168在食用油中的迁移研究

借助HPLC分析仪器试验研究了不同温度下聚烯烃抗氧剂1076和168向食用调和油、玉米油和菜籽油的迁移,讨论了不同油类、温度对迁移的影响,并将所得结果与用100%乙醇作为脂肪模拟物取得的结果进行对比.结果表明:油的种类对抗氧剂的迁移过程影响较小;温度对迁移动力学过程起到决定性作用,迁移速度随温度的升高而加快,达到迁移平衡所需的时间也越短;2种抗氧剂在食用油和100%乙醇中的迁移行为相似,总体说来100%乙醇可以作为脂肪模拟物来替代食用油用于抗氧剂的迁移试验研究.