Production, safety, health effects and applications of diacylglycerol functional oil in food systems: a review.

Diacylglycerol (DAG) is a world leading anti-obesity functional cooking oil synthesized via structural modification of conventional fats and oils. DAG exits in three stereoisomers namely sn-1,2-DAG, sn-1,3-DAG, and sn-2,3-DAG. DAG particularly sn-1,3-DAG demonstrated to have the potential in suppressing body fat accumulation and lowering postprandial serum triacylglycerol, cholesterol and glucose level. DAG also showed to improve bone health. This is attributed to DAG structure itself that caused it to absorb and digest via different metabolic pathway than conventional fats and oils. With its purported health benefits, many studies attempt to enzymatically or chemically synthesis DAG through various routes. DAG has also received wide attention as low calorie fat substitute and has been incorporated into various food matrixes. Despite being claimed as healthy cooking oil the safety of DAG still remained uncertain. DAG was banned from sale as it was found to contain probable carcinogen glycidol fatty acid esters. The article aims to provide a comprehensive and latest review of DAG emphasizing on its structure and properties, safety and regulation, process developments, metabolism and beneficial health attributes as well as its applications in the food industry.

The Synthesis of Organic Oils Blended Magnetorheological Fluids with the Field-Dependent Material Characterization.

Automation is one of the trending terminologies in the field of engineering to achieve various sensors and actuators such as the hydraulic system. Smart fluid is also one of the hot topics for researchers to develop a type of actuator in many control systems since the fluid's rheological characteristics can be controlled or tuned by the intensity of the external stimuli. In this work, a new smart fluid of magnetorheological (MR) fluid is proposed and its field-dependent rheological characteristics are experimentally identified. An MR fluid using the carrier fluid as the blend of three different fluids, namely silicon oil, honey, and organic oil is prepared. In addition, two types of natural oils are used, sunflower oil and cottonseed oil. The samples are prepared using the blend as the carrier fluid, electrolytic iron powder coated with guar gum as the dispersed phase, and oleic acid as an additive. The quantity of oleic acid is optimized for 30% by weight of electrolytic iron powder. Two samples based on sunflower and cottonseed oil are synthesized and characterized for shear viscosity and shear stress with respect to shear rate subjected to a variable magnetic field. The blend-based MR fluid shows about 10% improvement over the sedimentation rate of silicon oil-based MR fluid as compared to that to conventional MR fluid. The cottonseed oil blend-based MR fluid performs better than sunflower-based fluid in terms of the viscosity and structure.

Getting the Jump on the Development of Bullfrog Oil Microemulsions: a Nanocarrier for Amphotericin B Intended for Antifungal Treatment.

Amphotericin B (AmB), a potent antifungal drug, presents physicochemical characteristics that impair the development of suitable dosage forms. In order to overcome the AmB insolubility, several lipid carriers such as microemulsions have been developed. In this context, the bullfrog oil stands out as an eligible oily phase component, since its cholesterol composition may favor the AmB incorporation. Thus, the aim of this study was to develop a microemulsion based on bullfrog oil containing AmB. Moreover, its thermal stability, antifungal activity, and cytotoxicity in vitro were evaluated. The microemulsion formulation was produced using the pseudo-ternary phase diagram (PTPD) approach and the AmB was incorporated based on the pH variation technique. The antifungal activity was evaluated by determination of minimal inhibitory concentration (MIC) against different species of Candida spp. and Trichosporon asahii. The bullfrog oil microemulsion, stabilized with 16.8% of a surfactant blend, presented an average droplet size of 26.50 ± 0.14 nm and a polydispersity index of 0.167 ± 0.006. This system was able to entrap AmB up to 2 mg mL-1. The use of bullfrog oil as oily phase allowed an improvement of the thermal stability of the system. The MIC assay results revealed a growth inhibition for different strains of Candida spp. and were able to enhance the activity of AmB against T. asahii. The microemulsion was also able to reduce the AmB toxicity. Finally, the developed microemulsion showed to be a suitable system to incorporate AmB, improving the system's thermal stability, increasing the antifungal activity, and reducing the toxicity of this drug.

Ultrasound assisted synthesis of stable oil in milk emulsion: Study of operating parameters and scale-up aspects.

In the present work, application of ultrasound and stirring individually or in combination for improved emulsification of turmeric oil in skimmed milk has been investigated. The effect of different operating parameters/strategies such as addition of surfactant, sodium dodecyl sulfate (SDS), at different concentrations, quantity of oil phase, applied power, sonication time and duty cycle on the droplet size have been investigated. The stability of emulsion was analyzed in terms of the fraction of the emulsion that remains stable for a period of 28days. Optimized set of major emulsification process variables has been used at higher emulsion volumes. The effectiveness of treatment approach was analyzed based on oil droplet size, energy density and the time required for the formation of stable emulsion. It was observed that the stable emulsion at 50mL capacity with mean droplet diameter of about 235.4nm was obtained with the surfactant concentration of 5mg/mL, 11% of rated power (power density: 0.31W/mL) and irradiation time of 5min. The emulsion stability was higher in the case of ultrasound assisted approach as compared to the stirring. For the preparation of stable emulsion at 300mL capacity, it was observed that the sequential approach, i.e., stirring followed by ultrasound, gave lower mean droplet diameter (232.6nm) than the simultaneous approach, i.e., ultrasound and stirring together (257.9nm). However, the study also revealed that the simultaneous approach required very less time (15min) to synthesize stable emulsion as compared to the sequential approach (30min stirring and 60min ultrasound). It was successfully demonstrated that the ultrasound-assisted emulsification in the presence of SDS could be used for the preparation of stable turmeric oil-dairy emulsions, also providing insights into the role of SDS in increasing the stability of emulsions and of ultrasound in giving lower droplet sizes.

Lyotropic behavior of Gelucire 50/13 by XRD, Raman and IR spectroscopies according to hydration.

The present paper discuss the structural and vibrational properties of polyoxyethylene glycol glycerides (Gelucire 50/13) during the hydration with increasing water from 0% to 80%. The Gelucire 50/13 used as sustained release matrix forming agent in pharmaceutical applications and it was essentially studied by Small and Wide Angle X-ray Scattering (SWAXS), Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy according to the rate of hydration. The hydration behavior of this amphiphilic excipient has been investigated in the spectral range 4000-0cm-1 in Raman spectroscopy, and 4000-600cm-1 in FTIR. At increasing water contents Gelucire 50/13 forms successive bicontinuous to micellar supramolecular structures, and the vibrational changes were directly correlated with this conformational changes of the Gelucire structure. Overall, Raman and IR spectroscopy clearly demonstrated that the different functional groups studied could be characterized independently, allowing for the understanding of their role in Gelucire polymorphism.

Synergetic deoxy reforming of cellulose and fatty acid esters for liquid hydrocarbon-rich oils.

A series of liquid hydrocarbons (alkylbenzenes, alkanes, and alkenes) were obtained by a synergetic deoxy reforming (SDR) process of cellulose and linoleic acid methyl ester (LAME) at 350°C and 4-6MPa in a closed system without external source of hydrogen. The liquid product was obtained with a yield of 15wt% at a LAME/cellulose ratio of 0.2. In contrast, the direct deoxy reforming of cellulose produces oil that contains plenty of phenols and oxygen-containing compounds. Due to the insufficiency of water employed (30wt%), a radical reaction pathway was proposed. Quantum chemical calculations indicate that the radicals from LAME interfere with the reactions of the intermediate products from cellulose, being responsible for the removal of phenols and the formation of hydrocarbons. The SDR process offers an embryonic insight in an alternative technique for preparation of hydrocarbon fuels.

Efficient utilization of greenhouse gases in a gas-to-liquids process combined with CO2/steam-mixed reforming and Fe-based Fischer-Tropsch synthesis.

Two process models for carbon dioxide utilized gas-to-liquids (GTL) process (CUGP) mainly producing light olefins and Fischer-Tropsch (F-T) synthetic oils were developed by Aspen Plus software. Both models are mainly composed of a reforming unit, an F-T synthesis unit and a recycle unit, while the main difference is the feeding point of fresh CO2. In the reforming unit, CO2 reforming and steam reforming of methane are combined together to produce syngas in flexible composition. Meanwhile, CO2 hydrogenation is conducted via reverse water gas shift on the Fe-based catalysts in the F-T synthesis unit to produce hydrocarbons. After F-T synthesis, the unreacted syngas is recycled to F-T synthesis and reforming units to enhance process efficiency. From the simulation results, it was found that the carbon efficiencies of both CUGP options were successfully improved, and total CO2 emissions were significantly reduced, compared with the conventional GTL processes. The process efficiency was sensitive to recycle ratio and more recycle seemed to be beneficial for improving process efficiency and reducing CO2 emission. However, the process efficiency was rather insensitive to split ratio (recycle to reforming unit/total recycle), and the optimum split ratio was determined to be zero.

Bio oil synthesis by coupling biological biomass pretreatment and catalytic hydroliquefaction process.

The bio-oil synthesis from a mixture of wastes (7wt.% straw, 38wt.% wood, and 45wt.% grass) was carried out by direct liquefaction reaction using Raney Nickel as catalyst and tetralin as solvent. The green wastes were biologically degraded during 3 months. Longer the destructuration time; higher the yield into oil is. Biological pretreatment of green wastes promotes the liquefaction process. Among the components of degraded biomass, Humin, the major fraction (60-80wt.%) that was favored by the biological treatment, yields to a bio oil extremely energetic with a HHV close to biopetroleum (40MJ kg(-1)), contrariwise, Fulvic acids (2-12wt.%), the minor fraction is refractory to liquefaction reaction.

Evaluation of humic fractions potential to produce bio-oil through catalytic hydroliquefaction.

Humic substances were extracted from biodegraded lignocellulosic biomass (LCBb) and submitted to catalytic hydroliquefaction. The resulting bio-oils were compared with those of the initial biomass. Compared to fulvic and humic acids, humin presented a high conversion rate (74 wt.%) and the highest amount of liquid fraction (66 wt.%). Moreover it represented 78% of LCBb. Humin produced 43 wt.% of crude oil and 33 wt.% of hexane soluble fraction containing hydrocarbons which is a higher yield than those from other humic substances as well as from the initial biomass. Hydrocarbons were mainly aromatics, but humin produces the highest amount of aliphatics. Considering the quantity, the quality and the molecular composition of the humic fractions, a classification of the potential of the latter to produce fuel using hydroliquefaction process can be assess: Hu>AF>AH. The higher heating value (HHV) and oxygen content of HSF from humin were fully compatible with biofuel characteristics.

Development of a protocol to solidify native and artificial oil bodies for long-term storage at room temperature.

BACKGROUND: Oil bodies isolated from sesame seeds coalesced to form large oil drops when they were solidified in a drying process commonly used for food products. The aim of this study was to develop a protocol to solidify oil bodies for long-term storage at room temperature. RESULTS: On the basis of testing several excipients, the coalescence of oil bodies could be effectively prevented when they were combined with mannitol. Sizes of oil bodies appeared similar under a light microscope before and after powderisation in combination with 70% or more mannitol. Artificial oil bodies were successfully generated with sesame oil, phospholipid and recombinant sesame caleosin. Following the developed protocol, native and artificial oil bodies were stably solidified in tablets. Both native and artificial oil bodies dissolved from the tablets remained stable after an accelerated stress test under a condition of 75% humidity at 40 °C for 4 months. CONCLUSION: A protocol was successfully developed for the solidification of native and artificial oil bodies in stable powder and tablet forms. This successful protocol is very likely to expedite the utilisation of artificial oil bodies in their potential applications.

Effect of torrefaction on structure and fast pyrolysis behavior of corncobs.

Pretreatment of corncobs using torrefaction was conducted in an auger reactor at 250-300 °C and residence times of 10-60 min. The torrefied corncobs were fast pyrolyzed in a bubbling fluidized bed reactor at 470 °C to obtain high-quality bio-oil. The heating value and pH of the bio-oil improved when the torrefaction as pretreatment was applied; however, increasing bio-oil yield penalties were observed with increasing torrefaction severity. Fourier transform infrared Spectroscopy (FTIR) and quantitative solid (13)C nuclear magnetic resonance spectrometry (NMR) analysis of torrefied corncobs showed that the devolatilization, crosslinking and charring of corncobs during torrefaction could be responsible for the bio-oil yield penalties. Gas chromatography-mass spectrometry (GC-MS) analysis showed that the acetic acid and furfural contents of the bio-oil decreased with torrefaction temperature or residence time. The results showed that torrefaction is an effective method of pretreatment for improving bio-oil quality if the crosslinking and charring of biomass can be restricted.

Characteristics of products from fast pyrolysis of fractions of waste square timber and ordinary plywood using a fluidized bed reactor.

Fractions of waste square timber and waste ordinary plywood were pyrolyzed in a pyrolysis plant equipped with a fluidized bed reactor and a dual char separation system. The maximum bio-oil yield of about 65 wt.% was obtained at reaction temperatures of 450-500 °C for both feed materials. For quantitative analysis of bio-oil, the relative response factor (RRF) of each component was calculated using an effective carbon number (ECN) that was multiplied by the peak area of each component detected by a GC-FID. The predominant compounds in the bio-oils were methyl acetate, acids, hydroxyacetone, furfural, non-aromatic ketones, levoglucosan and phenolic compounds. The WOP-derived bio-oil showed it to have relatively high nitrogen content. Increasing the reaction temperature was shown to have little effect on nitrogen removal. The ash and solid contents of both bio-oils were below 0.1 wt.% due to the excellent performance of the char separation system.

Preparation and characteristics of bio-oil from the marine brown alga Sargassum patens C. Agardh.

The marine brown alga, Sargassum patens C. Agardh, floating on the Yellow Sea, was collected and converted to bio-oil through hydrothermal liquefaction with a modified reactor. A maximum yield of 32.1±0.2 wt.% bio-oil was obtained after 15 min at 340 °C, at a feedstock concentration of 15 g biomass/150 ml water, without using a catalyst. The bio-oil had a heating value of 27.1MJ/kg and contained water, lipid, alcohol, phenol, esters, ethers and aromatic compounds. The solid residue obtained had a high ash and oxygen content. The results suggest that S. patens C. Agardh has potential as biomass feedstock for fuel and chemical products.

Co-liquefaction of swine manure and crude glycerol to bio-oil: model compound studies and reaction pathways.

The reaction pathways of co-liquefaction of swine manure and crude glycerol to bio-oil (ester compounds) were investigated. Swine manure was hydrothermal treated (340 °C, 27.5 MPa, 15 min) with a number of model compounds in a high pressure batch reactor under inert atmosphere. The compounds were methanol, pure glycerol, mixture of pure glycerol, pure methanol and H(2)O, and commercial fatty acids (linoleic acid). The chemical composition of the bio-oil was analyzed by GC/MS. Glycerol, methanol and water showed synergistic effects on manure liquefaction, increasing the oil yield as high as 65%. A maximum oil yield of 79.96% was obtained when linoleic acid reacted with swine manure. Based on the results, the reaction pathways were proposed. Esterification reactions occurred not only because the crude glycerol have methanol, but also because methanol can be produced from hydrothermal reactions of glycerol.

Preparation and characterization of bio-oils from internally circulating fluidized-bed pyrolyses of municipal, livestock, and wood waste.

Fast pyrolyses of sewage sludge (SS), pig compost (PC), and wood chip (WC) were investigated in an internally circulating fluidized-bed to evaluate bio-oil production. The pyrolyses were performed at 500 °C and the bio-oil yields from SS, PC, and WC were 45.2%, 44.4%, and 39.7% (dried and ash-free basis), respectively. The bio-oils were analyzed with an elemental analyzer, Karl-Fischer moisture titrator, bomb calorimeter, Fourier transformation infrared spectrometer, gel permeation chromatograph, and gas chromatography/mass spectrometry. The results show that the bio-oil from SS is rich in aliphatic and organonitrogen species, while the bio-oil from PC exhibits higher caloric value due to its higher carbon content and lower oxygen content in comparison with that from SS. The bio-oils from SS and PC have similar chemical composition of organonitrogen species. Most of the compounds detected in the bio-oil from WC are organooxygen species. Because of its high oxygen content, low H/C ratio, and caloric value, the bio-oil from WC is unfeasible for use as fuel feedstock, but possible for use as chemical feedstock.

Effects of nitrogen source and concentration on biomass and oil production of a Scenedesmus rubescens like microalga.

This investigation examined the effects of nitrogen source and concentration on the ash free dry biomass (AFDB) and oil accumulation and productivity of a Scenedesmusrubescens like alga cultivated in indoor photo-bioreactors and outdoor raceway ponds. Among the nitrogen sources ((NH4)2CO3, urea, NaNO3, urea and NaNO3 mixture), the algae fed with the mixture of urea-N and NaNO3-N had the highest AFDB productivity of 0.539±0.040 g/L/d and the content of fatty acid methyl esters (FAME) (%) fed with (NH4)2CO3-N increased continuously for 17 days and reached 42.94±2.05% in the indoor photo-bioreactors. The content of C18 series (as % of total FAME) was high in all the treatments of nitrogen sources. The algae fed with (NH4)2CO3-N had the highest FAME productivity of 0.133 g/L/d (P<0.001). The effect of ammonia concentration on the AFDB and FAME productivity was also studied during the 20-day cultivation in the outdoor raceway cultivation system. The mean FAME of the algae cultivated in the ammonia concentration of 1.0-1.5 mg/L were the highest (0.556±0.112 g/m2/d) (P<0.001). The total Kjeldahl nitrogen (TKN) in the algae and cultivation water decreased but the FAME content (%) of the algae increased during the nitrogen starvation phase.

Bio-oil production via fast pyrolysis of biomass residues from cassava plants in a fluidised-bed reactor.

Biomass residues from cassava plants, namely cassava stalk and cassava rhizome, were pyrolysed in a fluidised-bed reactor for production of bio-oil. The aims of this work were to investigate the yields and properties of pyrolysis products produced from both feedstocks as well as to identify the optimum pyrolysis temperature for obtaining the highest organic bio-oil yields. Results showed that the maximum yields of the liquid bio-oils derived from the stalk and rhizome were 62 wt.% and 65 wt.% on dry basis, respectively. The pyrolysis temperatures that gave highest bio-oil yields for both feedstocks were in the range of 475-510 °C. According to the analysis of the bio-oils properties, the bio-oil derived from cassava rhizome showed better quality than that derived from cassava stalk as the former had lower oxygen content, higher heating value and better storage stability.

Role of clay minerals in oil-forming reactions.

Mineral-catalyzed decarboxylation reactions are important in both crude oil formation and, increasingly, biofuel production. In this study we examined decarboxylation reactions of a model fatty acid, propionic acid, C(2)H(5)COOH, to an alkane, C(2)H(6), in a model of pyrophillite with an isomorphic substitution of aluminum in the tetrahedral layer. We model a postulated reaction mechanism (Almon, W. R.; Johns, W. D. 7th International Meeting on Organic Geochemistry 1975, Vol. 7) to ascertain the role of Al substitution and a counterion in decarboxylation reactions. We employ a periodic cell, planewave, ab initio DFT computation to examine the total energies and the frontier orbitals of different model sets, including the effects of charge on the reaction, the effect of Al substitution, and the role of Na counterions. The results show that an uncharged system with a sodium counterion is most feasible for catalyzing the decarboxylation reaction in an Al-substituted pyrophillite and, also, that analysis of the orbitals is a better indicator of a reaction than charge alone.

Semi-solid state fermentation of sweet sorghum for the biotechnological production of single cell oil.

A semi-solid fermentation process for the production of biodiesel from sweet sorghum is introduced. The microorganism used is the oleaginous fungus Mortierella isabellina, which is able to transform efficiently sugar to storage lipid. Kinetic experiments were performed at various water content percentages. The fungus consumed simultaneously sugars and nitrogen contained in sorghum and after nitrogen depletion the biomass growth was completed and oil accumulation began. Water content of 92% presented the highest oil efficiency of 11 g/100 g dry weight of substrate. The semi-solid process is shown to have certain advantages compared to liquid cultures or solid-state fermentation and gives oil of high quality.

Biodiesel synthesis at high pressure and temperature: analysis of energy consumption on industrial scale.

Analysis of several different schemes for industrial FAME production at higher pressure and temperature (catalytic or non-catalytic synthesis) was realized with the aim to find the best route to reduce the energy consumption (EC) and to improve the life cycle energy efficiency. Obtained results indicated that the EC (MJ/kg FAME) mainly depends on degree of conversion of triglycerides being almost 25% smaller if degree of conversion increase from 97 mass% to complete conversion. Further significant decrease of EC might be obtained at subcritical conditions but only after substantial decrease of methanol to oil molar ratio (from 42 to 15) which requires use of appropriate catalyst. On account of that, the kinetics of heterogeneous catalyzed methanolysis of triglycerides was analyzed using data published in literature (CaO) as well as own experimental data (K(2)CO(3)/Al-O-Si) with a goal to obtain reliable kinetic rate constant which might be used for process simulation. This study shows that if heterogeneous process of biodiesel synthesis is realized at subcritical conditions then further decrease of EC is possible.