Natural Triglycerides Research Articles

Towards Photothermal Acid Catalysts Using Eco-Sustainable Sulfonated Carbon Nanoparticles—Part II: Thermal and Photothermal Catalysis of Biodiesel Synthesis

The main goal of this work is to evaluate the ability of sulfonated carbon nanoparticles (SCNs) to induce photothermal catalysis of the biodiesel synthesis reaction (transesterification of natural triglycerides (TGs) with alcohols). Carbon nanoparticles (CNs) are produced by the carbonization of cross-linked resin nanoparticles (RNs). The RNs are produced by condensation of a phenol (resorcinol or natural tannin) with formaldehyde under ammonia catalysis (Stober method). The method produces nanoparticles, which are carbonized into carbon nanoparticles (CNs). The illumination of CNs increases the temperature proportionally (linear) to the nanoparticle concentration and exposure time (with saturation). Solid acid catalysts are made by heating in concentrated sulfuric acid (SEAr sulfonation). The application of either light or a catalyst (SCNs) (at 25 °C) induced low conversions (<10%) for the esterification reaction of acetic acid with bioethanol. In contrast, the illumination of the reaction medium containing SCNs induced high conversions (>75%). In the case of biodiesel synthesis (transesterification of sunflower oil with bioethanol), conversions greater than 40% were observed only when light and the catalyst (SCNs) were applied simultaneously. Therefore, it is possible to use sulfonated carbon nanoparticles as photothermally activated catalysts for Fischer esterification and triglyceride transesterification (biodiesel synthesis).

Conversion of soybean oil under subcritical water conditions into liquid biofuels with low oxygen contents

Although the hydrotreatment of natural triglycerides is a well-established route for producing sustainable aviation fuel and renewable diesel, its high hydrogen consumption is a concern. The hydrothermolysis of natural triglycerides is considered a highly promising alternative route; however, the correlation between process parameters and fuel properties and detailed chemical structures of the produced fuel have not been established. Herein, we investigated the conversion of soybean oil to gasoline-, jet fuel- and diesel-fraction hydrocarbons with low oxygen contents. The properties of fuels produced under various reaction conditions were analyzed comprehensively using simulated distillation, total acid number (TAN), and elemental analysis. Under the optimized reaction conditions of 420 °C, 4.5 MPa, an oil-to-water ratio of 6:1, and reaction time of 10 min, 26 % gasoline-, 62 % jet fuel-, and 90 % diesel-range hydrocarbons with a low oxygen content of 5.1 %, low TAN of 0.04 mg KOH g−1, and high calorific value of 42.7 MJ kg−1 resulted. To elucidate the reaction mechanism, the liquid products produced from soybean oil were analyzed using comprehensive two-dimensional gas chromatography combined with time-of-flight mass spectrometry. In addition, based on the oleic acid conversion under varying hydrothermal conditions, we proposed deoxygenation, cracking, cyclization, and aromatization pathways. The findings of this study present possibilities for producing sustainable biofuels with low oxygen contents for the aviation industry.

Lipase and photodecarboxylase coexpression: A potential strategy for alkane-based biodiesel production from natural triglycerides

Lipase and photodecarboxylase coexpression: A potential strategy for alkane-based biodiesel production from natural triglycerides

Phase transfer of fatty acids into ultrasmall nanospheres for colorimetric detection of lipase and albumin.

Colorimetric detection of fatty acids during biological interactions is extremely difficult since they are optically silent. Here, fatty acids are found to function as ion-exchangers in ultrasmall polymeric nanospheres to facilitate the protonation of chromoionophores, causing a vivid color change between red and blue. With an excellent detection limit of 1.8 μg mL-1 for oleic acid, colorimetric assays for lipase and albumin are developed with quick response, high sensitivity, and low cost.

The influence of dietary fish oil on platelet composition in cardiac patients

Background and Aims: The habitual ingestion of fish is assumed to lower the incidence of coronary heart disease. Death from cardiovascular disease used to be rare among Inuits. It is suggested that C20:5 in the platelets is converted by the vascular-wall tissue to an anti-aggregatory prostacyclin. Partial dietary substitution of arachidonic acid by eicosapentaenoic acid may reduce the incidence of thrombotic disorders, including myocardial infarction. Recently high N-3 level fish oils in natural triglyceride form (20% docosahexanoic acid and 30% eicosapentanoic acid) were introduced.

Sustainable heterogeneously catalyzed single-step and two-step amide derivatives of non-edible natural triglycerides as dual-functional diesel fuel additives

In the present study, the 2.5-Li@CaO-Ca(OH)2-450 nanocatalyst (a mixture of Bronsted base Ca(OH)2 and Lewis base CaO) of 30−50 nm size nanoparticles was prepared by a simple wet-chemical method and utilized as a heterogeneous solid catalyst for the one-step and two-step amidation of non-edible high free fatty acids containing triglycerides (TGR) such as waste cooking oil (CO), Karanja oil (KO) and jatropha oil (JO). The 2.5-Li@CaO-Ca(OH)2-450 nanocatalyst took 45 min, 75 min, and 120 min for the complete one-step amidation (99 % yield) of CO, KO, and JO, respectively. In two-step amidation, the prepared nanocatalyst took 30 min and 45 min in the first step to prepare fatty acid methyl ester (FAME) and fatty acid ethyl ester (FAEE) from CO and then took 20 min and 30 min for complete amidation of FAME and FAEE. The first-order rate constants for the amidation of TGR, FAEE, and FAME were calculated as 0.10 min−1, 0.151 min−1, and 0.225 min−1, respectively. The 2.5-Li@CaO-Ca(OH)2-450 nanocatalyst was recycled and reused for ten reaction cycles for amidation and also found to complete amidation at room temperature (25−30 °C). The prepared amide derivative acted as a dual functional diesel fuel additive and found to improve the cetane number from 52.6 to 56.1 and lubricity from 460 to 247 μm of diesel fuel.

Abstract 6544: Macrocybin, a mushroom natural triglyceride, reduces tumor growth in vitro and in vivo through interference with the actin cytoskeleton

Abstract Mushrooms have been used for millennia in Eastern traditional medicine as cancer remedies and recent scientific studies have corroborated the presence of anticancer molecules in mushroom extracts. Our goal in this study was to screen a number of scarcely known mushroom species collected in the rain forest of Costa Rica looking for new antitumor molecules. Mushroom pieces were subjected to diverse extraction procedures involving water or ethanol at different temperatures. Extracts were screened using two human cell lines: A549 (lung adenocarcinoma) and NL20 (immortalized normal lung epithelium). Extracts able to kill tumor cells while preserving the integrity of non-tumor cells were considered “anticancer”. Positive extracts were fractionated with different techniques and the purification of the active compound was guided by its biological activity on the cell lines. When the compound was pure enough, its chemical structure was elucidated through nuclear magnetic resonance, mass spectrometry, and other ancillary techniques. The new molecule was synthesized and tested for biological activity both in vitro and in vivo with a xenograft assay. The mechanism of action was investigated through confocal microscopy, qRT-PCR, and Western blotting. The mushroom species with a better therapeutic window was Macrocybe titans, a local edible mushroom of very large proportions. The active ingredient was found in the precipitated phase of a 95% ethanol extraction with ultrasounds for 30 min, kept at -20°C for 24 h. To purify the active compound this extract was subjected to alkaloidal separation followed by column chromatography with polymeric resin (HP20-SS). The fraction obtained at pH 12 contained the active substance. Chemical analysis of the active molecule showed that it was a triglyceride containing oleic acid, palmitic acid, and a more complex fatty acid with 2 double bonds. Synthesis of all possible triglycerides with those characteristics and biological testing identified the natural compound as the R enantiomer of the triglyceride, which was named Macrocybin. A xenograft study showed that Macrocybin significantly reduces A549 tumor growth. In addition, Macrocybin treatment resulted in the dismantlement of the actin cytoskeleton in tumor cells (but not in normal cells). In conclusion, we have shown that the mushroom Macrocybe titans has anticancer properties and that the active principle is the new triglyceride, Macrocybin. This molecule constitutes a first-in-class new drug that works through the dismantlement of the actin cytoskeleton. Future experiments will establish the usefulness of Macrocybin for different types of cancer, either alone or in combination with other therapies. Citation Format: Marcos Vilariño, Josune García-Sanmartín, Laura Ochoa-Callejero, Rafael Peláez, Alfredo Martinez. Macrocybin, a mushroom natural triglyceride, reduces tumor growth in vitro and in vivo through interference with the actin cytoskeleton [abstract]. In: Proceedings of the Annual Meeting of the American Association for Cancer Research 2020; 2020 Apr 27-28 and Jun 22-24. Philadelphia (PA): AACR; Cancer Res 2020;80(16 Suppl):Abstract nr 6544.

Coproduction of Value-Added Lube Base Oil and Green Diesel from Natural Triglycerides via a Simple Two-Step Process

A versatile process for coproducing green diesel and value-added lube base oil from natural triglycerides (e.g., vegetable oil, waste cooking oil, and microalgal oil) was developed. The two-step reaction process comprises (i) thermal oligomerization of triglycerides via Diels–Alder and/or radical-mediated addition of the C═C bonds within the fatty acid units and (ii) catalytic deoxygenation of the oligomerized triglycerides via hydro-upgrading. Different triglyceride sources, that is, palm oil, soybean oil, and linseed oil, were investigated as the starting feedstock. Thermal oligomerization of the triglycerides at 300 °C proceeded at the expense of the C═C bonds within the unsaturated fatty acid units. Thus, the degree of triglyceride oligomerization was enhanced when the reactant triglycerides contained more unsaturated fatty acid units (palm oil < soybean oil < soybean + linseed oil < linseed oil). The oligomerized triglycerides were subsequently deoxygenated over a Pt-MoOx/TiO2 catalyst, which converted the oligomerized and monomeric fatty acid units into lube base oil (C30–C54) and green diesel (C15–C18) fractions, respectively. The produced lube base oils were completely saturated with very high viscosity indexes (>120) and a nondetectable sulfur content, which could meet the specifications of high-quality group III lube base oil.

Enzymatically derived oil-based L-ascorbyl esters: Synthesis, antioxidant properties and controlled release from cosmetic formulations

Lipase-catalyzed transesterification of vitamin C by natural triglycerides is promising approach for cost-efficient synthesis of liposoluble food and cosmetic antioxidants. Nevertheless, application of these alternative acyl donors is insufficiently explored, despite of their low price, wide abundance and possibility for obtaining versatile products. Within current study, fatty acid ascorbyl esters were synthesized from vitamin C and natural triglycerides (lard, sunflower, coconut and linseed oil) in a process catalyzed by immobilized lipase Novozym® 435 and their controlled release was examined. High conversions were achieved at optimized conditions, even at high substrate concentrations, thus high concentrations of acsorbyl-ester were synthesized using these natural lipids. All ester mixtures exhibited very high capacity for scavenging of DPPH radicals, among which linseed oil derived esters, with ascorbyl linolenate as prevailing compound, were the most efficient (IC50 0.663 μM), while coconut oil derived ester mixture (IC50 0.739 μM), composed predominantly of molecules with medium side chains, was second best. Coconut oil derived esters were successfully incorporated in typical cosmetic formulations for controlled release of bioactive compounds - O/W emulsion and gel-emulsion. Franz cell diffusion study demonstrated that esters release from mixture and two carrier systems was formulation dependent and revealed decrease of effective diffusivities with ester side acyl chain length increase. According to calculated effective diffusivity coefficients, faster trans-membrane delivery of the same molecule was achieved from gel-emulsion comparing to O/W emulsion. Applied approach enabled highly efficient cost-saving production of fatty acid ascorbyl esters, which could find direct application in various lipophilic products.

One‐pot solvent‐free transformation of natural triglycerides to ester and amide derivatives over CaO@KC nanostructured catalysts

One‐pot solvent‐free transformation of natural triglycerides to ester and amide derivatives over CaO@KC nanostructured catalysts

One-Pot Solvent-Free Synthesis of N,N-Bis(2-Hydroxyethyl) Alkylamide from Triglycerides Using Zinc-Doped Calcium Oxide Nanospheroids as a Heterogeneous Catalyst

N,N-Bis(2-hydroxyethyl) alkylamide or fatty acid diethanolamides (FADs) were prepared from a variety of triglycerides using diethanolamine in the presence of different transition metal-doped CaO nanocrystalline heterogeneous catalysts. The Zn-doped Cao nanospheroids were found to be the most efficient heterogeneous catalyst, with complete conversion of natural triglycerides to fatty acid diethanolamide in 30 min at 90 °C. The Zn/CaO nanoparticles were recyclable for up to six reaction cycles and showed complete conversion even at room temperature. The amidation reaction of natural triglycerides was found to follow the pseudo-first-order kinetic model, and the first-order rate constant was calculated as 0.171 min–1 for jatropha oil aminolysis. The activation energy (Ea) and pre-exponential factor (A) for the same reaction were found to be 47.8 kJ mol–1 and 4.75 X 108 min-1, respectively.

Evolving a lipase for hydrolysis of natural triglycerides along with enhanced tolerance towards a protease and surfactants.

In the accompanying paper, we described evolving a lipase to the point where variants were soluble, stable and capable of degrading C8 TAG and C8 esters. These variants were tested for their ability to survive in an environment that might be encountered in a washing machine. Unfortunately, they were inactivated both by treatment with a protease used in laundry detergents and by very low concentrations of sodium dodecyl sulfate (SDS). In addition, all the variants had very low levels of activity with triglycerides with long aliphatic chains and with naturally occurring oils, like olive oil. Directed evolution was used to select variants with enhanced properties. In the first 10 rounds of evolution, the primary screen was selected for variants capable of hydrolyzing olive oil whereas the secondary screen was selected for enhanced tolerance towards a protease and SDS. In the final six rounds of evolution, the primary and secondary screens identified variants that retained activity after treatment with SDS. Sixteen cycles of evolution gave variants with greatly enhanced lipolytic activity on substrates that had both long (C16 and C18) as well as short (C3 and C8) chains. We found variants that were stable for more than 3hours in protease concentrations that rapidly degrade the wild-type enzyme. Enhanced tolerance towards SDS was found in variants that could break down naturally occurring lipid and resist protease attack. The amino acid changes that gave enhanced properties were concentrated in the cap domain responsible for substrate binding.

Photoenzymatic Production of Next Generation Biofuels from Natural Triglycerides Combining a Hydrolase and a Photodecarboxylase

AbstractA photobiocatalytic cascade transforming natural triglycerides into alkanes/alkenes is proposed. Starting from natural triglycerides, free fatty acids have been obtained using lipases. The free fatty acids were then, in a photoenzymatic step, decarboxylated into the C1‐shortened alkanes using a recently described photodecarboxylase from Chlorella variabilis NC64A. This cascade produced alkanes from various natural (waste) oils in significant amounts (up to 24 g L−1) and may provide a basis for valorisation of waste oils into a next generation of biodiesel.

The bioavailability of eicosapentaenoic acid from reconstituted triglyceride fish oil is higher than that obtained from the triglyceride and monoglyceride forms.

Omega 3 fatty acids have healthcare benefits, but their absorption characteristics are not well defined, particularly for strategies to improve their bioavailability. We performed a double blind study comparing the bioavailability of 20% eicosapentaenoic acid in 4.5 grams of: natural triglyceride, reconstituted triglyceride, enzymatically synthesized triglyceride, monoglyceride and diglyceride. Seven healthy volunteers were given the supplements on five occasions while repeated measurements of eicosapentaenoic acid were taken to calculate the area under the curve for the next 24 hours. There was a significant difference between the mean of calculated area under the curve of eicosapentaenoic acid from reconstituted triglyceride (30.2) and that of the enzymatically synthesized triglyceride (11.9) and monoglyceride (13.4), z=-2.36 and -2.19, respectively, p<0.05. In summary, eicosapentaenoic acid bioavailability of chemically reconstituted triglycerides was better than that obtained from enzymatically synthesized triglyceride and monoglyceride.

Novel Approach for Flavonoid Esters Production: Statistically Optimized Enzymatic Synthesis Using Natural Oils and Application in Cosmetics

The present work describes application of natural triglycerides for lipase-catalyzed esterification of structurally diverse flavonoids—esculin, naringin, and phloridzin. Ester mixtures with laurate...

Effects of Fatty Acid Compositions on Heavy Oligomer Formation and Catalyst Deactivation during Deoxygenation of Triglycerides

Deoxygenation of triglycerides (e.g., vegetable and microalgae oils) through hydro-upgrading is one of the most important routes to produce oxygen-free hydrocarbon fuels from biomass. Even though natural triglycerides are composed of fatty acids of different structures, their effects on catalytic selectivity and deactivation during deoxygenation have not been comprehensively investigated. In this study, we used three different reactant triglycerides including palm oil, soybean oil, and linseed oil for catalytic deoxygenation over Pt/γ-Al2O3. These oils consist of fatty acids with increasing degrees of unsaturation in the order of palm oil (number of C═C per fatty acid: 0.55) < soybean oil (1.33) < linseed oil (2.18). The catalytic results showed that the increased unsaturation of the triglycerides caused enhanced formation of heavy products by oligomerization (mostly dimers) of unsaturated fatty acid derivatives through Diels–Alder reaction and/or radical addition. These heavy products were readily transf...

Upgrading Biodiesel from Vegetable Oils by Hydrogen Transfer to its Fatty Esters.

Conversion of vegetable-derived triglycerides to fatty acid methyl esters (FAMEs) is a popular approach to the generation of biodiesel fuels and the basis of a growing industry. Drawbacks of the strategy are that (a) the glycerol backbone of the triglyceride is discarded as waste, and (2) most available natural triglycerides in the U.S. are multi-unsaturated or fully saturated, giving inferior fuel performance and causing engine problems. Here we show that catalysis by iridium complex 1 can address both of these problems through selective reduction of triglycerides high in polyunsaturation. This is realized using hydrogen from methanol or those imbedded in the triglyceride backbone, concurrently generating lactate as a value-added C3 product. Additional methanol or glycerol as a hydrogen source enables reduction of corn and soybean oils to > 80% oleate. The cost of the iridium catalyst is mitigated by its recovery through aqueous extraction. The process can be further driven with a supporting iron-based catalyst for the complete saturation of all olefins. Preparative procedures are established for synthesis and separation of methyl esters of the hydrogenated fatty acids, enabling instant access to upgraded biofuels.

Mo promoted Ni-Al2O3 co-precipitated catalysts for green diesel production

Three Mo promoted Ni-Al2O3 co-precipitation catalysts with practically the same composition (49–52%wtNi, 6-7%wtMo) were prepared using three different co-precipitation modes: co-precipitation at room temperature using ammonia as precipitating agent as well as co-precipitation at higher temperature (110 °C) using ammonia or urea as precipitating agent. The corresponding un-promoted catalysts were also synthesized for comparison. The catalysts were exhaustively characterized using various techniques and evaluated for the selective deoxygenation (SDO) of natural triglycerides using two different feedstocks: sunflower oil (SO) and waste cooked oil (WCO). The catalytic tests were performed under solvent free conditions in a semi-batch reactor at 310 °C, hydrogen pressure 40 bar and very high reactant volume to catalysts mass ratio (100 mL/1 g).The promoting action of the Mo(VI) and Mo(IV) well dispersed oxidic phases, was demonstrated in all cases. This was attributed to the impressive decrease in the size of the nickel nanoparticles and to the inhibition of the formation of the catalytically inactive nickel aluminate. Moreover, the Mo (VI) and Mo(IV) oxidic phases affect the network of the SDO favoring the hydrodeoxygenation of the intermediate alcohols with respect to the decarbonylation of intermediate aldehydes.The catalyst prepared at high co-precipitation temperature using ammonia as precipitating agent was proved to be the most efficient for the SDO of SO. An almost complete transformation of SO into n-C15, n-C16, n-C17, n-C18 (green diesel: 97% of liquid products) was obtained under the above mentioned conditions. This catalyst was proved to be very stable. The catalyst prepared at room co-precipitation temperature using ammonia as precipitating agent was proved to be the most efficient for the SDO of WCO (green diesel: 76% of liquid products). Its improved efficiency with respect to the other Mo promoted catalysts was attributed to its smaller pore size which prohibits the blockage of active sites located inside the corresponding pores by bulky compounds present in WCO.

Thermal Ageing of Some Insulating Fluids in Contact with Insulation Paper and Copper

The behaviour of copper and insulation paper in various electrical insulating fluids (transformer oils) exposed to thermal ageing at 110�30C for 1000 hours in closed vessels (without access to atmospheric oxygen) has been studied. The processing of the comparative experimental data revealed in all cases that the concentration of dissolved oxygen in the investigated oils decreases exponentially during the heat treatment. In the presence of the copper foil, the oxygen is almost depleted (the dissolved oxygen concentration is approaching zero), indicating a higher affinity of the copper to oxygen than the affinity to oxygen of the investigated oils. In the presence of the copper foil and / or of the insulation paper, the degradation processes of the mineral oils have a pronounced character, explained by the catalytic activity of the Cu2O film that has been formed and by the paper degradation, respectively. A high thermo-oxidative stability was noticed in the case of natural triglyceride oils, particularly for the synthetic ester-based oil.

A Continuous and Sensitive Spectrophotometric Assay for Lipase and Phospholipase A Activities Using α-Eleostearic Acid-Containing Substrates.

To date, several sensitive methods, based on radiolabeled elements or sterically hindered fluorochrome groups, are usually employed to screen lipase and phospholipase A (PLA) activities. Here, a new ultraviolet spectrophotometric assay for lipase or PLA was developed using natural triglycerides or synthetic glycerophosphatidylcholines containing α-eleostearic acid (9Z, 11E, 13E-octadecatrienoic acid) purified from Aleurites fordii seed oil. The conjugated triene present in α-eleostearic acid constitutes an intrinsic chromophore and consequently confers strong UV absorption properties of this free fatty acid as well as of lipid substrates harboring it. The substrate was coated into the wells of a microplate, and the lipolytic activities were measured by the absorbance increase at 272nm due to the transition of α-eleostearic acid moiety from the adsorbed to the soluble state. This continuous assay is compatible with a high-throughput screening method and can be applied specifically to the screening of new potential lipase, PLA1 and PLA2 inhibitors.