The Effect of Addition of High-Melting Monoacylglycerol and Candelilla Wax on Pea and Faba Bean Protein Foam-Templated Oleogelation

Use of oleogels prepared from hydrocolloids has recently gained considerable attention as an alternative for trans and saturated fats. Lately, pulse proteins such as faba bean protein and pea protein have been successfully used to prepare oleogels using a foam-templated approach. Although the pulse proteins are healthy oleogelators, high oil loss and low quality of cake baked using pulse protein-stabilized oleogels due to its poor rheological properties challenged its use. The present study explored whether the addition of small amount of high-melting monoglyceride (MAG) or candelilla wax (CW) can be used to improve the oil binding capacity, rheological properties, and baking qualities of pulse protein-stabilized oleogels composed of 5% faba bean or pea protein concentrate with 0.25% xanthan gum foams. Different concentrations (0.5–3%) of MAG or CW were dissolved in canola oil at 80 °C, followed by addition into the freeze-dried protein-polysaccharide foams (pH 7) and quickly transferred to a refrigerator to facilitate the formation of oleogels. The crystallized additives were found to be reinforcing the protein foam network in the oleogels. With increase in concentration of CW and MAG, the oil binding capacity, firmness, cohesiveness, and storage moduli of the oleogels were increased. Oleogels with and without MAG or CW were then characterized and tested for their performance as a shortening replacer in model baked cakes. Findings showed improved textural properties of cake upon addition of MAG in the foam-templated oleogels, however, compared to the shortening, negative effect on cake hardness and chewiness was still observed with the oleogels.     

Effects of fatty acid and emulsifier on the complex formation and in vitro digestibility of gelatinized potato starch

The effects of fatty acid, monoacylglycerol, and polyglycerol fatty acid ester with varying chain length in their acyl chains on the extent of complex formation (complex index) and in vitro enzymatic digestibility of gelatinized potato starch were investigated. The complex index increased with increase in the concentration of the ligands (fatty acid, monoacylglycerol, and polyglycerol fatty acid ester), with the plateau in the complex index value depending on the type of ligands. In comparison of complex index among fatty acid-samples, the complex index maximum increased as the chain length increased up to octanoic acid and then decreased. In comparison of complex index among fatty acid-, monoacylglycerol-, and polyglycerol fatty acid ester-samples at each acyl chain, the complex index maximum followed the order polyglycerol fatty acid ester > monoacylglycerol > fatty acid. Fatty acid, monoacylglycerol, and polyglycerol fatty acid ester with long acyl chains greatly reduced the enzymatic hydrolysis of starch. Polyglycerol fatty acid ester with palmitic acid chains was the strongest inhibitor of starch hydrolysis, suggesting that further complex formation may occur during the hydrolysis of gelatinized starch (enzyme-annealing).     

Differential Scanning Calorimetric Study of Solidification Behavior of Monoacylglycerols to Investigate the Cold-Flow Properties of Biodiesel

Monoacylglycerols (MAG) are impurities present in biodiesel as a result of incomplete reactions. MAG often solidify in biodiesel even at room temperature because of their high melting points. This worsens the cold-flow properties such as the cloud point and pour point. We hypothesized that several types of MAG solidify simultaneously; therefore, we performed differential scanning calorimetry of binary mixtures of MAG to elucidate their interactions during solidification. Three thermodynamic formulas were then applied to the experimental results: (1) non-solid-solution, (2) solid-solution, and (3) compound formation models. Binary mixtures of MAG showed complicated liquidus curves with multiple upward convex shapes, with which only the compound formation model fitted well. This model was applied to multicomponent mixtures that consisted of MAG and fatty acid methyl esters (FAME) as surrogate biodiesel fuels. We confirmed that the model still worked well. The results show that the compound formation model has good potential for predicting the cold-flow properties of biodiesel.     

Zn-Mg复合氧化物催化大豆油甘油解合成单甘酯

采用共沉淀法制备了一系列不同Zn、Mg物质的量比的Zn-Mg复合氧化物,将其用于催化大豆油甘油解合成单甘酯(MG),采用XRD、氮气吸附-脱附仪、SEM、TEM对Zn-Mg复合氧化物结构与性能进行了表征,并测定了催化剂的表面碱强和碱量。优化了合成单甘酯的工艺条件,并考察了Zn-Mg复合氧化物的重复使用性能。结果表明,改变Zn、Mg物质的量比不仅可以调控Zn-Mg复合氧化物的碱强与碱量,还可以调控其比表面积、孔容等结构参数;不同Zn、Mg物质的量比复合氧化物的催化活性变化趋势与其碱强度(H)在15.0H17.2间碱量变化趋势相一致;n(Zn)/n(Mg)=0.1时,复合氧化物(ZM0.1)具有最好的催化甘油解反应活性;使用该催化剂合成单甘酯的适宜条件为:n(甘油)∶n(大豆油)=3∶1,反应温度210℃,反应时间2 h,催化剂用量为大豆油质量的0.6%,该条件下大豆油转化率达95.6%,单甘酯收率为58.5%。ZM0.1催化剂重复使用4次时大豆油转化率仍达80.9%。     

Comparative Thermal Characteristics and Fatty Acid Composition of Mono- and Diacylglycerols of Lard and Some Commercial Emulsifiers

A study was carried out to compare the fatty acid composition and thermal profiles of mono- and diacylglycerols of six commercial emulsifiers, coded as E1, E2, E3, E4, E5, and E6, purchased from different manufacturers with those of the same derived from lard. The lipid extraction from the commercial emulsifiers was done using the Soxhlet method and the isolation of individual mono- and diacylglycerols was carried out using a column chromatographic method. The isolated partial acylglycerols of lard and individual emulsifiers were subjected to fatty acid analysis by gas chromatography and thermal analysis by differential scanning calorimetry. A clear distinction between lard-based emulsifier and the commercial emulsifiers was achieved by the application of principal components analysis to the fatty acid data. According to thermal analysis, mono- and diacylglycerols of lard displayed significant differences from those of commercial mono- and diacylglycerols with respect to the thermal transitions in the cooling curves. This study concluded that partial acylglycerols of none of the commercial emulsifiers employed in this study displayed similarity to those of lard-based emulsifiers.     

Influence of Solid Supports on Acyl Migration in 2-Monoacylglycerols: Purification of 2-MAG via Flash Chromatography

Soybean oil 2-monoacylglycerol (2-MAG) was synthesized via the Novozym 435-catalyzed ethanolysis of triacylglycerols and purified by conventional liquid–liquid extraction. The 2-MAG was subjected to incubation at 20 and 40 °C in the presence of five solid commercial support materials, Lewatit, Silica Gel 60, Alumina–Neutral Brockman Activity 1, Amberlyst-15, and SBA-15, to determine their effects on acyl migration rates. Lewatit and SBA-15 did not catalyze acyl migration rates after 144 h, while silica gel slightly increased migration rates. The more polar alumina and the cationic Amberlyst 15 significantly increased migration rates. Flash chromatography purification of 2-MAG using silica gel as the immobile phase developed with an acetone/hexane binary gradient proved to be a comparable purification method to liquid–liquid extraction, resulting in 60 % 2-MAG yield, no residual triacylglycerol, diacylglycerol, or glycerol co-products, and a 95 mol% 2-MAG purity vs. 1-MAG, demonstrating that flash chromatography did not catalyze acyl migration.     

High Sn-2 Docosahexaenoic Acid Lipids for Brain Benefits,and Their Enzymatic Syntheses: A Review

The normal development and maintenance of central neural functions are highly correlated with the amount of docosahexaenoic acid (DHA; ω-3 fatty acid) accumulated in the brain. DHA incorporated at the sn-2 position of lipids is well absorbed by intestinal mucosa and utilized efficiently in vivo. However, modern consumers have a reduced direct intake of DHA and increased intake of saturated fats or ω-6 fatty acid oils, resulting in behavioral and neurophysiological deficits. To provide an understanding of the integrated beneficial effects of DHA on the human brain, this review introduces the positional difference (sn-2 and sn-1,3 positions) of DHA on a glycerol skeleton in natural fats and oils, and further discusses the possible functional mechanism regarding DHA supplementation and the gut–brain axis. The multiple bidirectional routes in this axis offer a novel insight into the interaction between DHA supplementation, the gut microbiota, and brain health. To achieve high sn-2 DHA in diets, it is suggested that sn-2 DHA lipids be enzymatically produced in more efficient and economical ways by improving the specific activities of lipases and optimizing the purification procedures. These types of diets will benefit individuals with strong needs for sn-2 ω-3 lipids such as infants, children, and pregnant and lactating women.     

Synthesis,Purification, and Acyl Migration Kinetics of 2-Monoricinoleoylglycerol

2‐Monoricinoleoylglycerol (2‐MRG) was synthesized by the Novozym 435 catalyzed alcoholysis of castor oil in excess ethanol (1:70 mol:mol) at ambient temperature. Due to the fatty acid C12‐OH group, conventional liquid–liquid extraction methods developed for less polar, non‐hydroxylated 2‐monoacylglycerols (2‐MAG) proved inadequate for 2‐MRG purification. Alternatively, 2‐MRG was purified by normal‐phase flash chromatography (FC) on silica gel using a binary acetone‐hexane gradient mobile phase. Gram quantities of 2‐MRG were isolated in 63 % yield and contained no residual diacylglycerol (DAG), which fail to separate using liquid–liquid extraction methods. The 2‐MRG was obtained at ~90 mol% relative to 1‐MRG, proving that the FC method did not appreciably catalyze acyl migration. ¹H‐NMR spectroscopy was used to monitor the spontaneous acyl migration of isolated 2‐MRG from 20 to 80 °C. The relative energy of activation calculated from the Arrhenius relationship of the 2‐MRG acyl migration rate constants was 82.9 kJ/mol. This was ~two‐fold higher than the theoretical ΔG_298.15 calculated from molecular modeling using density functional calculations (B3LYP/6?31 + G*) of 2‐MRG, the ketal ring transition state, and 1‐monoricinoleoylglycerol (1‐MRG). The synthesis and isolation methods reported herein provide a convenient means to access useful intermediates for functionalized structured lipids.