Sophorolipid-Derived Unsaturated and Epoxy Fatty Acid Estolides as Plasticizers for Poly(3-Hydroxybutyrate)

Unsaturated and epoxy fatty acid estolides were synthesized from the ω and ω‐1 hydroxy fatty acids derived from sophorolipids (SL). These estolides were utilized as additives in solution‐cast poly(3‐hydroxybutyrate) (P3HB) films and their plasticizing effects reported. Estolides in the P3HB film matrix resulted in slight reductions of melting and glass transition temperatures while the crystallinity remained relatively constant (±2.0 %). Scanning electron microscopy revealed irregular film surfaces in the presence of both estolides and the formation of pores within the P3HB film matrix. These irregularities influenced the tensile properties of the films by incrementally decreasing the tensile strength and moduli of the P3HB films and increasing their elongation. Curing the films for 3 months in the presence of estolide triggered an enhanced tensile strength and modulus when compared to the initial films. Irradiation was implemented in an attempt to crosslink the estolides. Results showed that radiation did not result in crosslinking but rather instigated chain scission and reduced the molecular weights by up to 81 % which further reduced the tensile strength, elongation and modulus of the P3HB films. These tensile property variations showed that while the tensile strength of the P3HB films declined in the presence of both estolides, the plasticity and elongation improved validating that these unique SL‐derived estolides can be effectively used as plasticizers in P3HB films.     

Investigation of Oil and Protein Contents of Eight Sudanese Lagenaria siceraria Varieties

The composition of the oil and protein contents of eight Lagenaria siceraria varieties was characterized in order to evaluate their suitability as a source of edible oil and protein. The physicochemical properties and fatty acids of seed oils were determined. The oil yield ranged from 24.11 to 26.32 %. The refractive indices and relative densities of the oils fell within the narrow ranges of 1.464–1.468 and 0.857–0.907 g/cm³, respectively. The saponification value ranged from 158.48 to 179.52 mg KOH/g, unsaponifiable matter was between 0.749 and 0.937 %, and the peroxide values were lower than Codex values for vegetable oils. The principal fatty acids were linoleic (62.1–67.9 %), oleic (11.54–15.46 %), palmitic (12.13–14.03 %), and stearic (6.71–7.71 %) acids. Low linolenic acid levels were also observed (<1 %) within the range of 0.32–0.44 %. The major essential amino acids were arginine (2.04–3.77 g/100 g), leucine (1.245–1.726 g/100 g), phenylalanine (0.803–1.396 g/100 g), and lysine (0.921–1.383 g/100 g). The non‐essential amino acids were glutamic acid (2.5–4.37 g/100 g), aspartic acid (1.39–2.36 g/100 g), serine (0.69–1.19 g/100 g), glycine (0.79–1.37 g/100 g), alanine (0.72–1.37 g/100 g), and proline (0.63–1.02 g/100 g). Nine minerals (Na, Ca, Mg, K, Cu, Fe, Mn, Zn, and P) were determined with significant (p < 0.05) differences. The studied oils showed promising results and can be used in the food, cosmetics, and pharmaceutical industries. This is the first study on the eight L. siceraria seed varieties grown in Sudan, opening the way for further studies on these seeds.     

Retardation of Crystallization of Diacylglycerol Oils Using Polyglycerol Fatty Acid Esters

Liquid oil containing high concentrations of diacylglycerols (DAG > 80 %, hereafter referred to as DAG-rich oil) is generally more likely to cause precipitation at chilled temperatures (clouding phenomena) than triacylglycerol-based oil. The clouding phenomena that occur during long-term storage of DAG-rich oil are unwanted in consumer products and therefore, must be prevented. In the present study, we attempted to retard precipitation by adding food emulsifiers, polyglycerol fatty acid esters (PGFE) containing different fatty acid moieties. DSC, polarized optical microscopy, and X-ray diffraction studies revealed that the addition of 0.2 % PGFE containing palmitic and oleic acid moieties very effectively retarded precipitation in the DAG-rich oil. To confirm these observations, we prepared a model DAG oil to mimic DAG-rich oil and examined the retardation behavior of high-melting DAG fractions using PGFE. The results are discussed in terms of the effects of PGFE additives on the pre-nucleation processes of high-melting fractions in DAG-rich oil.     

Synergistic Effects of Antioxidants on the Oxidative Stability of Soybean Oil- and Poultry Fat-Based Biodiesel

Biodiesel is an alternative fuel composed of saturated and unsaturated methyl ester fatty acids that is very prone to oxidation attack. Exposure to air, heat, light, and metallic contaminants can lead to autoxidation, and the degradation of fuel properties such as kinematic viscosity and total acid number. This study examines the effectiveness of blends of primary antioxidants from combinations of butylated hydroxyanisole (BHA), propyl gallate (PG), pyrogallol (PY) and tert-butyl hydroquinone (TBHQ) to increase oxidative stability. Results indicate that binary antioxidant formulations: TBHQ:BHA, TBHQ:PG and TBHQ:PY were most effective at 2:1, 1:1, 2:1 weight ratio, respectively in both distilled soybean oil- (DSBO) and distilled poultry fat- (DPF) based biodiesel. Antioxidant activity increased as the loadings were increased. The synergisms of the antioxidant pairs were different with different biodiesel types, suggesting a dependence on the fatty acid methyl ester (FAME) composition. The best synergistic effect was observed with the TBHQ:BHA blends while the best stabilization factors (SF) were achieved by using the TBHQ:PY blends. Quantification of antioxidant content in stored biodiesel with TBHQ:PY blend demonstrates that the main factor of synergy is the regeneration of PY by TBHQ.     

Detailed Compositional Analysis of Vegetable Oil Metathesis Products Using Microfluidic Switching Multidimensional Gas Chromatography

Olefin metathesis provides an attractive and versatile route for the catalytic transformation of triglyceride‐based fats and oils into renewable chemical intermediates. Cross‐metathesis reaction of triglycerides with α‐olefins followed by transesterification leads to a complex array of olefins, fatty acid methyl esters, and fatty acid dimethyl esters. In order to evaluate the commercial value of these mixtures and to optimize process conditions, it is necessary to obtain detailed, quantitative, compositional information. With standard, one‐dimensional, gas chromatographic approaches, complete resolution of all components of interest with short analysis times is difficult to achieve. In this report we describe a rapid, microfluidic, two‐dimensional gas chromatographic methodology suitable for the detailed componential analysis of these complex mixtures. The precision of this method for individual components, as measured by the relative standard deviation, is on the order of 1 % or less, and the recovery of known blends of esters and olefins averaged 100 %.     

Feruloylated Products from Coconut Oil and Shea Butter

The synthesis of feruloylated coconut oil and feruloylated shea butter were demonstrated in 0.5-L scale, shaken, batch reactions. Ethyl ferulate and the vegetable oil/fat were combined in a 1.0:1.3 mol ratio in the presence of Candida antartica lipase B immobilized on an acrylic resin (Novozym 435) at 60 °C. The transesterification of ethyl ferulate with coconut oil and shea butter reached equilibrium conversions, after 22 days, of 63 and 70%, respectively, with the shea butter transesterifications producing a white precipitate not observed in the coconut oil transesterifications. The faster transesterification rates, equilibrium conversions and white precipitate were shown to result from di- and monoacylglycerols (DAG and MAG) present in the shea butter. The transesterification of ethyl ferulate and coconut oil was also tested in a continuous, enzymatic, packed-bed bioreactor using Novozym 435 at 60 °C to produce feruloylated coconut oil at rates of 0.5–0.9 kg/day over 4.5 months. The feruloylated coconut oil acylglycerol species were identified by LC–MS analysis of transesterification reactions of ethyl ferulate with medium chain triacylglycerol (TAG) standards, C8–C14. The feruloylated vegetable oils possessed an ultra violet (UV) absorbing λ _max 328 nm, making them good UVAII absorbers, as defined by the U.S. Food and Drug Administration. The feruloylated coconut oil possessed a 17.5% higher absorption capacity than feruloylated shea butter on a per weight basis. All the feruloylated vegetable oils possessed rapid antioxidant capacity (50% reduction of initial radical concentration <5 min) at the concentrations tested, 0.5–2.5 mM. Feruloylated coconut oil possessed chemical and physical characteristics that suggested it would be fungible for feruloylated soybean oil in current retail formulations.     

A Sustainable Process for the Production of Varnishes Based on Pelargonic Acid Esters

This work demonstrates the possibility of using pelargonic acid (PA) esters as solvents for vegetable-based varnishes. First, PA was efficiently produced through a chemocatalytic cleavage of oleic acid, practicing an optimized scale-up of previously developed conditions. PA was then esterified with several alcohols ROH (R = Me, i-Pr, n-Bu, n-Hex, 2-ethylhexyl, and sec-octyl) and the products were formulated with a commercial rosin (Phenolic Modified Rosin Esters). Dynamic light scattering (DLS) measures and determination of rheological parameters of the corresponding varnishes disclosed their suitability for applications in offset, coldset, heatset printing inks, and coatings. Furthermore, inks obtained were used to efficiently produce preliminary industrial offset prints.     

Antioxidant Activity of Osage Orange Extract in Soybean Oil and Fish Oil during Storage

The food industry is seeking natural antioxidants for edible oils that have comparable activity to synthetic counterparts. In this study, Osage orange extract (OOE) rich in osajin (42.9%) and pomiferin (30.0%) was obtained after hexane extraction of the fruit, and its antioxidant activity was examined in stripped soybean oil (SBO) and fish oil (FO), in which antioxidants and polar compounds were removed. The antioxidant activity of OOE was compared with commercial natural antioxidants (i.e., rosemary extract and mixed tocopherols) and a synthetic antioxidant, butylated hydroxytoluene (BHT), during storage at 25 and 40 °C. The 0.1% OOE had stronger antioxidant activity than 0.1% rosemary extract and 0.1% mixed tocopherols in both oils at 25 and 40 °C. Its activity was similar to 0.02% BHT in SBO and was similar or slightly stronger than 0.02% BHT in FO. When OOE was studied at 0.05, 0.1, and 0.2%, there was a weak dose–response in SBO but a stronger dose–response in FO. Headspace volatile analysis using solid phase micro-extraction (SPME) combined with GC–MS indicated that 0.1% OOE was very effective in preventing the formation of volatile oxidation products in both oils. Although it should be further tested for safety before the actual use, this study shows that OOE can be developed as an antioxidant for edible oils.     

Antioxidant Efficacy of a New Synergistic,Multicomponent Formulation for Fish Oil Omega-3 Concentrates

Today, tocopherols serve as the industrial standard antioxidant protection for fish oil omega-3 concentrates. Synergistic interactions between tocopherols, ascorbyl palmitate and natural polyphenols extracted from plant sources have been demonstrated in model systems. The main goal for this work was to develop a mix of such antioxidants with improved efficacy in the context of preserving industrial marine oil concentrates. The antioxidant formulation comprises tocopherols, ascorbyl palmitate, rosemary extract and green tea catechins. Part of the scope was to develop a method for dissolving green tea catechins in oil. The key element of the method is to introduce green tea on a lipid insoluble carrier when dissolving the extract in the oil, and thereafter remove the carrier by filtration. The antioxidant mix was tested against tocopherol in omega-3 concentrates of minimum 300 mg/g eicosapentaenoic acid (EPA) plus 200 mg/g docosahexaenoic acid (DHA) in the form of triacylglycerides and ethyl esters. The mix was superior compared to tocopherols in suppressing both primary- and secondary oxidation. Weight increase measurements of oil in contact with air correlated well with standard oxidation tests within individual samples and the method was considered simple and useful for monitoring oxidation in omega-3 concentrates.     

Deterioration Kinetics of Crude Palm Oil,Canola Oil and Blend During Repeated Deep-Fat Frying

The oxidation of vegetable oils is generally treated as an apparent first order kinetic reaction. This study investigated the deterioration of crude palm oil (CPO), refined canola oil (RCO) and their blend (CPO:RCO 1:1 w/w) during 20 h of successive deep‐fat frying at 170, 180 and 190 °C. Kinetics of changes in oil quality indices, namely, free fatty acid (FFA), peroxide value (PV), anisidine value (p‐AV), total polar compounds (TPC) and color index (CI) were monitored. The results showed that FFA and PV accumulation followed the kinetic first order model, while p‐AV, TPC and CI followed the kinetic zero order model. The concentration and deterioration rate constants k, increased with increasing temperatures. This effect of temperature was modeled by the Arrhenius equation. The results showed that PV had the least activation energies E_a (kJ/mol) values of 5.4 ± 1 (RCO), 6.6 ± 0.7 (CPO) and 11.4 ± 1 (blend). The highest E_a requirement was exhibited by FFA with a range of 31.7 ± 3–76.5 ± 7 kJ/mol for the three oils. The overall E_a values showed that the stability of the blend was superior and not just intermediate of CPO and RCO. The correlation of the other oil quality indices with TPC indicated a positive linear correlation. The p‐AV displayed the strongest correlation, with mean correlation coefficient r_s of 0.998 ± 0.00, 0.994 ± 0.00 and 0.999 ± 0.00 for CPO, RCO and blend, respectively.     

Influence of Sophorolipid Structure on Interfacial Properties of Aqueous-Arabian Light Crude and Related Constituent Emulsions

Sophorolipids (SLs) offer an “environmentally friendly” alternative to chemically produced surfactants currently used in formulations for crude oil extraction, processing, and reclamation. Studies herein describe how sophorolipid structure influences its interfacial properties for environmentally and industrially relevant oil–water systems where the oil phase is Arabian light crude oil, paraffin oil, decane, hexadecane, a 1:1 vol/vol mixture of o-xylene and 1,2-dimethylcyclohexane, or a mixture of paraffin oil, o-xylene, and 1,2-dimethylcyclohexane (synthetic crude oil). SL-hexyl ester (SL-HE) reduces the crude oil–water interfacial tension (IFT) by 57 and 91% at 0.001 and 0.5 mg/mL, respectively. Crude oil displacement tests reveal that SL-ethyl ester (SL-EE) and SL-HE contract a crude oil slick on water to about 20% of its starting volume allowing for easier burning of spilled crude oil on marine surfaces. Water retention and emulsion phase (e.g., o/w vs. w/o) are determined by SL-structure/concentration, oil concentration, and oil composition to understand their performance for crude oil transportation and clean-up. For the first time, w/o emulsions were obtained using SLs and their formation occurred after homogenization when the oil phase consisted of a 1:1 mixture of o-xylene and 1,2-dimethylcyclohexane. Generally, the performance of SL-esters in the above studies was superior to that using Triton X-100, a comparison nonionic surfactant. Hence, SL-esters offer a valuable platform for tuning interfacial properties to optimize surfactant performance.     

Chemical Composition and Characteristics of <Emphasis Type="Italic">Commiphora wightii</Emphasis> (Arnott) Bhandari Seed Oil

The seeds of Commiphora wightii (Arnott) Bhandari contain 9.8 ± 0.7% oil. The fatty acid composition and chemical properties of the extracted oil were determined. Gas liquid chromatography of the methyl esters of the fatty acids shows the presence of 46.62% saturated fatty acids and 51.40% unsaturated fatty acids. The fatty acid composition is as follows: capric acid 3.50%, myristic acid 14.51%, palmitic acid 6.68%, stearic acid 4.70%, arachidic acid 3.18%, behenic acid 14.05%, myristoleic acid 1.34%, palmitoleic acid 12.07%, oleic acid 14.15%, eicosenoic acid 0.11%, linoleic acid 22.34% and alpha linoleic acid 1.37%.     

Thermal and Textural Properties of Organogels Developed by Candelilla Wax in Safflower Oil

We investigated organogel formation in dispersions of CW in safflower oil (SFO). Candelilla wax (CW) has as its main component hentriacontane (78.9%), a n-alkane with self assembly properties in organic solvents (i.e., vegetable oils). Results showed that, independent of the cooling rate (i.e., 1 °C/min and 10 °C/min) and gel setting temperature (T _set), the CW organogels observed a thermoreversible behavior. This was evaluated by the behavior of thermal parameters that characterized organogel formation (gelation temperature, T _g; heat of gelation, ΔH_g) and melting (melting temperature, T _p; heat of melting, ΔH_M) after two heating-cooling cycles. For a given CW concentration (i.e., 0.5, 1.0, and 3%), the magnitude of ΔH_M and T _p and the structural organization of the organogel, depended on the cooling rate, the thermodynamic drive force for gelation, and the annealing process occurring at high T_set (i.e., 25 °C). At T _set of 25 °C the microplatelet units that formed the organogel aggregated as a function of storage time, a process that resulted in an increase in organogel hardness. In contrast, at T _set of 5 °C annealing occurred in a limited extent, but gels had higher solid fat content and microplatelet units of a smaller size than the gels obtained at 25 °C. The result was a three-dimensional network with greater hardness than the one obtained at 25 °C. The 3% CW organogels showed no phase separation up to 3 months at room temperature, with textures of potential use by the food industry.     

Rapid FT-NIR Analysis of Edible Oils for Total SFA, MUFA, PUFA, and Trans FA with Comparison to GC

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.     

Development of Rigorous Fatty Acid Near-Infrared Spectroscopy Quantitation Methods in Support of Soybean Oil Improvement

The mature seeds of soybean (Glycine max L. Merr) are a valuable source of high‐quality edible lipids and protein. Despite dramatic breeding gains over the past 80 years, soybean oil continues to be oxidatively unstable, due to a high proportion of polyunsaturated triacylglycerols. Until recently, the majority of soybean oil underwent partial chemical hydrogenation. Mounting health concerns over trans fats, however, has increased breeding efforts to introgress mutant and biotechnological genetic alterations of soybean oil composition into high‐yielding lines. As a result, there is an ongoing need to characterize fatty acid composition in a rapid, inexpensive and accurate manner. Gas chromatography is the most commonly used method, but near‐infrared reflectance spectroscopy (NIRS) can be calibrated to non‐destructively phenotype various seed compositions accurately and at a high throughput. Here we detail development of NIRS calibrations using intact seeds for every major soybean fatty acid breeding goal over an unprecedented range of oil composition. The NIRS calibrations were shown to be equivalent to destructive chemical analysis, and incorporation into a soybean phenotyping operation has the potential to dramatically reduce cost and accelerate phenotypic analysis.     

Effect of different cell disruption methods on lipid yield of Schizochytrium sp.

In this study, it was investigated to increase the lipid yield of the microalgae Schizochytrium sp., by applying different cell disruption methods; acid treatment with HCl, osmotic shock, enzyme applications and ultrasonic homogenizer were combined with the Bligh and Dyer or Soxhlet methods. In the Soxhlet method, the lipid and fatty acid yields decreased due to the inability of the method to break down the lipid cells sufficiently and the high temperature application. Enzyme application (hemicellulase treatment at 55°C for 2 days) prior to Bligh and Dyer method (BDE) was found more efficient in terms of lipid and DHA yield compared to other methods. BDE process increased the lipid yield to 21.72 ± 0.74% and DHA content to 19.25 ± 0.09% from lipid yield of 18.87 ± 0.4% and DHA content of 18.41 ± 0.20% by the Bligh and Dyer control (BDC). Major saturated fatty acids were 14:0, 16:0, 18:0, 24:0 and the highest saturated fatty acid was 16:0 (palmitic acid). Lipid health indices such as n-6/n-3, PUFA/SFA, atherogenicity index, thrombogenicity index and hypocholesterolemic/hypercholesterolemic ratios were almost favorable. With this study, appropriate lipid extraction methods were studied to provide an economical and environmental friendly suggestion for future studies to be used in areas such as food, feed and cosmetics grade. It was concluded that the most convenient method among the cell disruption methods was BDE owing to lipid and fatty acid yield.     

Tandem Mass Spectrometric Determination of Glycolipids in Wheat Endosperm: A New Tool for Breeders to Rank and Select Early Seed Generations

Wheat breeding for end-use quality is enhanced by development and application of a selective and sensitive method for ranking early generation cultivars as part of the effort of generating desirable wheat lipids. A desirable wheat lipid, the increased concentration of which in hard wheat flour correlates positively with bread loaf volume, is digalactosyldiglyceride (DGDG). A mass spectrometric test for DGDG was applied to 100-mg samples of flour isolated from the F6 generation of hard winter wheats. The test enables prediction of desirable lipids in early generations so that decisions about the F6 progeny improve wheat breeding efficiency. Previous attempts to screen wheat cultivars for desirable glycolipids were constrained by sample size, lipid extraction and purification, and time. Here, we present flour glycolipid data obtained from individual wheat plants grown in short rows in two nurseries. The endosperm (100 mg) representing several kernels was exhaustively extracted with a total lipid solvent. Following isolation of the lipids and addition of an internal standard, the lipids were subjected to tandem mass spectrometry (MS–MS). The concentration of DGDG in the flour from five to seven kernels was found to vary by a factor of two within single nurseries. Thus, early generation lipid screening enables informed selection for this hard wheat quality indicator.     

Physicochemical and Rheological Properties of Crystallized Blends Containing <Emphasis Type="Italic">trans</Emphasis>-free and Partially Hydrogenated Soybean Oil

Three vegetable oil blends, intended for formulation of high melting temperature confectionary coatings, were prepared by mixing different proportions of coconut oil, palm stearin, and either partially hydrogenated soybean oil (PH-SBO) or native soybean oil (i.e., trans-free SBO). The blends were crystallized under the same isothermal conditions and the crystallized systems evaluated by DSC, SFC, polarized light microscopy, and rheology under low [i.e., G′ and yield stress (σ*)] and high (i.e., creep and recovery profiles) stress forces. Overall, all trans-free blends showed lower SFC and heat of crystallization than the ones obtained with PH-SBO blends. These results showed that trans-fatty acids decrease the level of structural order of the crystals, and probably also the organization of the crystal network. As a result, most of the crystallized blends with PH-SBO showed lower σ* values and higher creep profiles (i.e., softer texture) than trans-free blends, particularly in systems crystallized at high supercooling and blends with saturated medium chain TAG. Nevertheless, at particular crystallization temperatures some trans-free formulations provided crystallized systems with rheological properties that would result in softer textures than the ones obtained with PH-SBO blends. Knowledge of the rheological properties under low and high stress forces is vital when comparing the functionality of crystallized TAG systems with and without TAG with trans-fatty acids.     

Quantification and Determination of Composition of Steryl Ferulates in Refined Rice Bran Oils Using an UPLC-MS Method

Gamma-oryzanol contains a mixture of steryl ferulates found in rice bran oil. Several studies have attributed nutraceutical properties to this mixture, such as hypocholesterolemic and anti-inflammatory activities. A method based on ultra-performance liquid chromatography coupled with electrospray ionization mass spectrometry was developed and evaluated for the simultaneous quantification of gamma-oryzanol and identification of five major steryl ferulates directly in refined rice bran oils (RBO) samples. The proposed method was evaluated according to linearity by obtaining standard curves with R ² values above 0.990, and limit of detection values ranged from 1.9 to 5.9 µg/mL, whereas limits of quantification ranged from 5.9 to 17.9 µg/mL; inter- and intraday accuracy and precision were within the range required by the US Food and Drug Administration guidelines; recovery levels ranged from 78 to 85% for gamma-oryzanol, and from 84 to 119% for steryl ferulates. The method can be considered robust in relation to the NH₄OH (ammonium hydroxide) content and cone voltage variations, with coefficient of variation and average relative percentage deviation values lower than 7.0 and 4.4%, respectively. The stability during the storage test was maintained in concentrated samples (18.5 µg/mL), with recovered values between 93 and 113%. This method was successfully applied to the analysis of RBO samples, demonstrating that it could be easily used for quality control purposes.