Protein from camelina seed is a valuable co-product that can be derived from the meal remaining after oil extraction. The current study describes the types and physicochemical properties of the major proteins present in camelina meal. Seed coat mucilage, which interferes with protein extraction, was removed from whole seeds by digestion with Viscozyme® and lipids were removed with hexane to obtain demucilaged/defatted meal. Protein comprised 51.3% of meal dry matter and the eight essential amino acids comprised 40.8% of total amino acids. The meal polypeptide profile showed bands originating from cruciferin (~44.1 and 51.7 kDa), napin (~14 kDa) and oil body proteins (OBP; ~15-20 kDa) resembling that of other crucifers. Cruciferins (11 isoforms) were the predominant proteins, while vicilins (6 isoforms) also were identified among the proteins soluble at pH 8.5. Among the proteins soluble at pH 3, napins (5 isoforms) comprised the majority, though late embryogenesis abundant proteins also were found. Camelina cruciferin and napin were confirmed to possess predominantly β-sheet and α-helix secondary structures, respectively. Camelina cruciferin structure was highly sensitive to changes in medium pH and underwent acid-induced denaturation at pH 3, but exhibited high thermal stability (>80°C) at neutral and alkaline pHs. The structure of camelina napins was less sensitive to pH. The major proteins associated with oil bodies were oleosins (6 isoforms). Identification and characterization of the properties of camelina meal proteins will enable strategic paths for co-product valorization.

Oxidative polymerization of plant oils and lipids is poorly understood yet widely encountered. Oil oxidation is accelerated at high temperatures, typically above 110°C, where tri-acylglycerides are converted into toxic compounds and viscous deleterious polymers. Polymerization of mono-unsaturated oil (210°C, 3h, open to air) was investigated by comparing four similar sized molecules with different functional groups: oleic acid, methyl oleate, trans-7-tetradecene and stearic acid. Non-volatile products identified by NMR spectroscopy are minor ketones for saturated fatty acid (stearic acid), epoxides for acyl chains without acid groups (methyl oleate, tetradecane) and copious oligomerization, through ester cross-links, for acyl chains with acid and olefinic groups (oleic acid). Long range C-H coupling clearly shows ester (not ether) cross-links, contradicting long held beliefs. Chain fragmentation also occurs as revealed by species with methylene groups bonded to oxygen, -CH2-O-C(=O)-R. Large size (slow diffusion) of the first oligomer (trimer) formed by thermal oxidation of oleic acid, (representing hydrolyzed vegetable oil) was evidenced by DOSY (diffusion ordered spectroscopy). Since the first oligomers formed still have reactive groups (olefin, carboxylic acid), poly-ester formation is inevitable at longer oxidation times. Model oil reactions monitored by NMR spectroscopy are important for resolving the complex chemistry of vegetable oil polymerization.

Oil bodies (OBs) are micron- or submicron-sized sub-organelles widely found in plants seeds and nuts. The structure OBs is composed of a core of triglycerides covered by a phospholipid-protein layer, which ensures the stability of the OBs under extreme environmental conditions and further protects core lipids as energy reserves. As naturally pre-emulsified oil-in-water emulsions, OBs have been gradually applied to replace synthetically engineered oil droplets. In this paper, the recent research on the composition, extraction, stability, delivery system, digestion, food applications and future perspectives of plant OBs are reviewed. Recent studies have focused on the OBs surface protein identification and function, large-scale extraction techniques such as enzyme assisted, high pressure, ultrasound, and extrusion and the reconstituted OBs. Electrostatic deposition of polysaccharides significantly improves the stability of OBs emulsions. OBs emulsions have promising applications to encapsulate bioactive compounds, deliver targeted drugs, and prepare gels and edible functional films. The digestive behavior of OBs emulsions is similar to that of protein-stabilized emulsions, which can increase the satiety, effectively help reduce calorie intake and improve the bioavailability of functional factors. It has also promoted the development of simulated dairy, spices and meat products.

The present study investigated the effect of solid-state fermentation (SSF) of cold-pressed (CP) and hexane-extracted (HE) canola meals with Aspergillus niger NRRL 334 and A. oryzae NRRL 5590 on the functionalities of protein products extracted from them. After SSF, proteins were recovered using alkaline extraction-isoelectric precipitation (AE-IP) or salt extraction-dialysis (SE). SSF of the two meal types reduced the protein content of the extracts produced by AE-IP. There were varied effects to solubility, foaming, and emulsifying properties as a result of SSF under the combined influence of functionality pH, strain, meal type, and protein extraction method. The protein isolate produced from CP meal using SE had increased solubility at pH 7 (from 51.8 to 90.7%) when the meal was fermented with A. oryzae. Both strains resulted in an over 2-fold increase in the emulsifying activity index (at pH 7) of AE-IP products from CP meal. For both protein extraction methods, the protein products from A. niger fermented HE meal had better foaming capacity (FC) at pH 7 than the controls (non-fermented), but reduced FC at pH 3. Overall, regardless of meal fermentation, the SE products were richer in protein and had higher oil holding capacity (OHC), whereas the water holding capacity (WHC) was higher for AE-IP isolates. SSF of the meals generally improved the O/WHC of the extracted proteins. The findings suggest that canola protein functionality could be effectively modulated by SSF with different microbial strains under various processing conditions to enhance their applicability in the food industry.

Bigels, are prepared by homogenization of an organogel and hydrogel. Bigels can offer improved properties when compared to other gelled systems due to its semi-solid internal phase and supramolecular interactions between components. The objective of this study was to determine the effect of mono-diglycerides (MDG) on the supramolecular structure and interactions, physical stability and mechanical properties of a rice bran wax (RBW)–gelatin bigels. The organogel-to-hydrogel (OG:HG) ratios tested were 60:40, 70:30 and 80:20 with MDG incorporated at four concentrations (0.5, 1, 2, 3% (w/w)). Bigels were analyzed using nuclear magnetic resonance spectroscopy (NMR), confocal scanning laser microscopy (CSLM), Fourier transform infrared spectroscopy (FTIR), texture analysis and liquid binding capacity studies. The results showed that MDG have a dual effect on the structural organization and stability of the systems; they act as emulsifiers and/or crystallization modifiers. CSLM and FTIR showed that the addition of MDG had the greatest effect on the microstructure of the 60:40 OG:HG ratio, where MDG concentrations 0.5 and 1% (w/w) exhibited a reduction in the size of the oleogel regions while concentrations 2 and 3% (w/w) showed a phase inversion. MDG addition resulted in a gradual decrease in bigel hardness, but an enhancement of physical stability.

We studied the thermomechanical and microstructural properties of oleogels developed with 2.1 to 15.7 Moles of monoglycerides/Mole of lecithin (MG/LC). The oleogels were developed (15°C) in vegetable (VO) and mineral (MO) oils using at each MG/LC 2% or 4% total mass of gelator. During oleogelation a synergistic MG-LC interaction existed deriving in the development of MG-LC cocrystals even below the gelators’ minimum gelling concentration. The cocrystals delayed the Lα→β polymorphic transition and worked as an active filler of the oleogels’ crystal network. In the VO, the oil with the highest relative polarity, the oleogels were structured by a network of β crystals where the cocrystals acted as an active filler. In the MO, the oil with the lowest relative polarity, the cocrystals’ development was favored while the Lα→β transition occurred just in the 15.7 MG/LC oleogels. Then, at all MG/LC the VO oleogels with 2% or 4% total gelator concentration achieved higher G’ than MO oleogels. However, the presence of β crystals will produce deleterious effects in shorter time in the VO oleogels than in the MO oleogels. In both oils the oleogels with the highest G’ and gel-like rheological behavior were achieved at 8.1 MG/LC, particularly at 4% total gelator concentration. Under these conditions the β polymorph was limited developed in the VO oleogels and completely absent in the MO oleogels. Then, we might tailoring the rheology of MG-LC oleogels with storage stability using as design variables the MG/LC, the total gelator concentration, and the polarity of the oil.

Odd chain fatty acids (C15:0 and C17:0) from dairy fat as well as odd chain phenolic lipids (alkylresorcinols) from whole grain are commonly reviewed as candidate biomarkers for dietary analysis and their ingestion are inversely related to chronic disease risks. Therefore, low levels of dietary intake of these odd chain molecules may be related to higher risk of physiological states that cause chronic diseases or mortality. It is a prerequisite to examine and understand their main role in beneficial health effects in disease prevention. We propose odd chain fatty acids (OC-FA) and most importantly odd chain phenolic lipids (OC-PL) as potential essential dietary compounds since they play key roles in physiological mechanisms. This review evaluates potential roles of OC-FA and OC-PL in mitigating chronic diseases in vitro and in vivo studies to support our hypothesis for odd chain molecules as essential dietary lipids. Further studies are needed to investigate the relationship between reduced intake of OC-FA and OC-PL containing foods and susceptibilities to chronic diseases.

The goal of the present study is to demonstrate 1H LF-NMR time relaxation measurements for efficient and rapid evaluation of Omega-3 polyunsaturated fatty acids (PUFA)-rich linseed oil (LSO) oxidative aging mechanisms, by monitoring primary chemical and structural changes occurring during thermal oxidative stress. The LF NMR monitors the different proton spin-spin coupling energy relaxation times, T2 within LSO molecular segments, from the initiation of free radical generation and hydroperoxide formation to the propagation of alkoxy radicals, and alpha, beta-unsaturated aldehydes formation, and a termination phase of crosslinked polymerization end products. The 1H LF NMR T2 values monitors both the covalent and secondary bonding interactions (e.g., electrostatic and hydrogen bonding) during the different oxidation phases. The present paper shows that LSO tail segments mobility in terms of T2 multi-exponential relaxation decays, generated by data reconstructing of 1H transversal relaxation components are providing a clear, sharp and informative understanding of LSO sample’s autoxidation aging processes. This is supported by high field band selective 1H NMR pulse excitation for hydroperoxide and aldehydes quantification of the same LSO samples at 25, 40, 60, 80, 100, and 120oC with pumped air for 168 h. Peroxide value, viscosity and self-diffusion, as well as fatty acids profile and by- products determined by GC-MS were also carried out, and correlated with the LSO tail T2 relaxation results. In conclusion the selective determination of LSO alkyl tail T2 energy relaxation time domain values was demonstrated as a rapid evaluation marker for following omega-3 PUFA-rich oils oxidative aging.

This work presents an original approach to develop an integrated process to improve the nutritional characteristics of natural oils, starting with the extraction from the raw material by environmentally friendly methods and following with the production of novel acylglycerols using immobilized lipases. Specifically, 2-monoacylglycerols (2-MAGs) enriched in the omega-3 stearidonic acid (SDA) were synthesized by selective ethanolysis of extracted Echium plantagineum oil using the lipase from Thermomyces lanuginosus (TLL). Different reaction conditions were investigated to minimize the undesirable acyl migration and to ensure the purity of final products. The biocatalyst produced in our laboratory by the immobilization of TLL on a hydrophobic support reached the maximum theoretical amount of 2-MAG in only 2 h at mild reaction conditions, achieving a product enriched in omega 3 SDA (up to 25%). Moreover, the produced biocatalyst exhibited higher stability than commercial lipases. The average activity after 5 cycles was 71%, allowing several reutilization cycles and developing a feasible enzymatic process. Finally, 2-MAGs was used as starting material to synthesize structured triacyclglycerols (STAGs) in solvent-free systems. The use of molecular sieves in combination with the immobilized lipase from Rhizomucor miehei (RML) showed to be an extraordinarily fast strategy to produce pure STAGs (100% in 1h), 4 times higher than the activity showed by the commercial derivative. Thus, the enzymatic processes developed in this study open a range of possibilities to synthesize omega-3 acylglycerols with improved characteristics for essential biological functions and nutritional advantages, proving the usefulness of immobilized lipases to produce novel functional lipid.

Novel cocoa butter equivalents were designed using dry fractionated Pequi oil and solvent fractionated Kpangnan butter. Static crystallization of binary mixtures of these two fractions into the triclinic form (β2) was achieved after 12 days for all mixtures and after 4 days for the 80:20 w/w and 90:10 w/w fractionated Kpangnan:Pequi oil mixtures. Moreover, after 60 days of storage at 22oC, all binary blends (except 100% fractionated pequi oil and 100% fractionated Kpangnan butter) were crystallized in the most stable triclinic crystal form (β1). Here we also discovered an unusual melting behavior for the fractionaled 30:70 w/w and 20:80 w/w fractionated Kpangnan:Pequi oil mixtures, where after 4 days of static crystallization at room 22oC, these mixtures displayed higher than predicted melting points, 41.89 oC and 33.32 oC, respectively. This suggested a faster kinetics of transformation to the triclinic β2 form for those mixtures. Our results suggest that the 30:70 w/w fractionated Kpangnan:Pequi oil mixture with a melting point of 34oC after 60 days storage at 22oC, a stable triclinic β2 form, and a triglyceride composition of 28% POP, 4.6% POS and 33% SOS displayed solid state characteristics, melting point and crystal structure, of a commercial cocoa butter equivalent.

De-oiled canola meals are sources of protein-containing flavor-active phenolic compounds. Conventional canola oil processing utilizes an excess amount of solvents and is associated with the release of high-intensity bitter flavor-active phenolic compounds, limiting the use of the canola meal. Recent advances in the extraction and isolation of the bitter favor-active phenolic compounds from canola by-products produce protein isolates, however, would benefit the industry by producing a side-stream ingredient rich in phenolics. High temperature and pressure-aided processing, namely the accelerated solvent extraction (ASE) was investigated to extract the flavor-active bitter molecules from the canola meal. The extractability of flavor-active phenolic compounds including the major sinapates, kaempferol derivatives, and other thermo-generative compounds including thomasidioc acid (TA) was evaluated. The effects of temperature, solvent extractant and concentration, and the particle size of the meal, were examined on the extraction efficiency of these phenolic compounds. Extraction temperature (180oC) was the primary determinant (p<0.05) for the attenuation of major sinapates including sinapine and sinapic acid. Both ethanol and methanol extractants at a concentration of 70% (v/v) significantly (p<0.05) extracted the flavor-active phenolic compounds. The pressurized high temperature through optimized ASE conditions attenuated the bitter undesirable flavor-active phenolic molecules from canola meal thereby facilitating a potential value-added phenolic-rich by-product.

Previous studies reported that several amino acids had strong antioxidant activity in vegetable oils under frying conditions. In this study, the carboxylic acid group of amino acids was converted to a carboxylate group (-COO-Na+ or -COO-K+), a heating study was conducted with amino acid salts in soybean oil at 180 ºC. Sodium salts of amino acids including alanine, phenylalanine, and proline and disodium glutamate had significantly stronger antioxidant activity than the corresponding amino acids, and potassium salts had stronger antioxidant activity than sodium salts. Potassium salts of alanine and phenylalanine more effectively retained tocopherols in soybean oil than the corresponding amino acids during heating. Phenylalanine potassium salt had stronger antioxidant activity than phenylalanine in other vegetable oils including olive, high oleic soybean, canola, avocado, and corn oils. Phenylalanine potassium salt at 5.5. mM more effectively prevented oil oxidation than tert-butyl hydroquinone (TBHQ), a synthetic antioxidant, at its legal concentration limit (0.02%) indicating its feasibility as a new antioxidant for frying.

Cold-pressed hempseed oil (HSO) is known to have many health benefits due to many phytochemicals and high polyunsaturated fatty acids content. In this study, HSO oleogels were prepared with 3, 5, and 7% natural waxes including sunflower wax (SW), rice bran wax (RBW), beeswax, and candelilla wax to evaluate their potential as solid fat replacements in margarines and spreads. Firmness, crystal structures, and melting properties of these oleogels were evaluated. In general, wax-based HSO oleogels except for RBW-HSO oleogels had lower firmness and weaker crystal network than the corresponding soybean oil (SBO) oleogels. In contrast, RBW-HSO oleogels had similar firmness, comparable or stronger crystal network, and higher melting and crystallization enthalpies compared to those of SBO oleogels. After removing polar compounds from HSO, waxes except for RBW provided oleogels with greater firmness, higher melting and crystallization enthalpies, and stronger crystal network. Therefore, it was concluded that polar compounds negatively affected the physical properties of wax-HSO oleogels but not those of RBW-HSO oleogels. Margarine samples were prepared with SW- and RBW-HSO oleogels, and their firmness and melting properties were examined. The firmness of these margarines indicated that wax-HSO oleogels may achieve the firmness of commercial spreads with less than 3% wax while the firmness of stick margarines cannot be achieved even with 7% wax. Although the properties of wax-HSO oleogels should be further improved, they showed potential as solid fat replacements in margarines and spreads.

The extraction of butter from cocoa seeds involves various processing steps that weak the lipid-storing cell walls of cocoa cotyledons. Roasting is particularly critical, making cocoa nibs porous and brittle. In this study, the degree of disruption of the microstructure of cocoa nibs, and the quality and aroma profile of cocoa butter, were evaluated using two roasting techniques, forced convective oven, and fluidized bed. Fluidized bed roasting, recognized for its energy efficiency and low-footprint synthesis, was more than 10 times faster than oven roasting. This technique allowed a fast release of steam when parenchyma cell walls were still in a glassy state, while oven roasting caused gradual physical modification allowing the cell wall to become more elastic. Consequently, when using fluidizing bed technique, small pores of unroasted cocoa nibs swelled and coalesced to produce more large-sized ones. 3-D microscopic image analysis showed a total porosity in unroasted cocoa beans of 8.5 ± 2.0% (v/v): this value doubled upon oven roasting and triplicated upon fluidized bed roasting. The higher porosity in fast-roasted nibs was reflected in the lowest densities and highest cocoa butter yield. Cocoa butter obtained from fluidized-bed roasted cocoa showed a higher presence of pyrazines and 3-methylbutanal, and a lower concentration of hydroperoxides, thus enhancing the chocolate flavor and quality. In this paper, we showed that pore-structure of cocoa nibs is a key quality descriptor of roasting processing, and we concluded by energetic and quality considerations that fluidized bed roasting of cocoa nibs should be preferred over conventional roasting.

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 ℃. 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 ℃. 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.

Globally, there is an increasing demand for sources of plant-based protein. While Brassica napus L. is an important oilseed crop worldwide, there is also interest in improving its ability to serve as a valuable source of plant-based protein. Cruciferin, a seed storage protein that makes up 60% of the protein found in mature seeds of B. napus, is of interest for human consumption as a source of protein and as an ingredient in food products due to its functional properties. Existing methods for quantification of cruciferin protein are often time consuming and destroy the seed. This study explored the potential for the measurement of cruciferin protein content in whole seeds of B. napus by near-infrared spectroscopy (NIRS), to allow for efficient and non-destructive screening of breeding material. An enzyme-linked immunosorbent assay (ELISA)-based reference method was utilized to assess cruciferin content in a diverse population of B. napus. Scanning of whole seed samples produced spectra that were used to develop NIRS calibration equations. Statistical analysis of the calibration results indicated that the NIRS equations developed are poorly suited for prediction of cruciferin content.

Seeds of Lithospermum officinale L. from different climatic zones were analyzed looking for new sources γ-linolenic acid (GLA, 18:3n-6) and stearidonic acid (SDA, 18:4n-3). Cultured B. officinalis was also analyzed with comparative purposes. Analyses were conducted for fatty acid (FA) profiles in the whole seeds and in the neutral and polar lipids by GC; lipid classes by open column chromatography and preparative TLC; and tocopherols, sterols and phenolic compounds by HPLC-DAD, and the later compounds were confirmed by LC-MS. The richest GLA sample was L. officinale from St. Petersburg Botanical Garden (17.9% of total FA), while wild-growing L. officinale from the Rostov region showed the highest percentage of SDA (17.2% of total FA). Total FA content ranged from 11.3 to 20.8% of seed weight. Neutral and polar lipids accounted for ~98 and 2.27% of total lipids. Five neutral lipid classes were identified (% of NL): triterpene esters, 1.3; triacylglycerols, 93.1; free FA, 1.8; diacylglycerols, 1.4; and monoacylglycerols, 2.4. Tocopherols and sterols reached 35.7 and 83.8 mg/100 g seeds; γ-tocopherol was the main tocopherol detected, and Δ5-avenasterol was the predominant sterol. L. officinale seeds contain high amounts of phenolic compounds (389.9 mg/100 g as upper limit), in which rosmarinic acid was the main component. Overall, all data suggest the possibility of using L. officinale seed oil in pharmaceutical and cosmetic formulae and as functional food.

The initial oleogelation process (microstructuring) as well as the formulation are determinant to obtain the desired characteristics in oleogels with potential application in the industry. The microstructuring process in oleogels has been extensively studied by means of techniques highly sensitive to thermal variations, such as differential scanning calorimetry (DSC). However, there are other readily available techniques and equipment that can be employed to perform similar evaluations. Non-isothermal nucleation kinetics by spectrophotometric methods can be used as alternatives to basic crystallization studies in oleogels. Therefore, in this research a comparison of both techniques is presented, highlighting their similarities, advantages and limitations, in the study of the microstructure of oleogels. Oleogels were obtained with a minimum concentration of gelator and another saturated one, using vegetable oils of different degrees of saturation. The crystallization profiles of the oleogels were obtained by DSC, a non-isothermal nucleation kinetics was performed from the molten system and the final microstructure was evaluated by optical microscopy. The Fisher-Turnbull and Avrami model was used to evaluate the behavior during microstructuring. A gap was observed during the crystallization process by DSC which can be evaluated by spectrophotometry. Differences in the microstructuring process were found in both methods due to the temperature ramp used and formulation variables. The results obtained by spectrophotometry indicate that it can be a good alternative, easily accessible in oleogel crystallization studies, when high sensitivity or very specific thermal parameters are not required.