Fatty Acid Diesters Research Articles

Synthesis and Study of Mixed Diesters of Synthetic Petroleum Acids and Fatty Acids

The paper deals with the synthesis and study of mixed (unsymmetrical) 1,4-butanediol diesters of petroleum acids and aliphatic fatty acids (С6–С8). High yield of the target product (90.3%) was reached under the following conditions: temperature 110–120°С, catalyst amount 1.3 wt % (based on the acid), acid : alcohol molar ratio 2 : 1.4. The physicochemical parameters and structures of the products were determined. The mixed 1,4-butanediol esters obtained are well compatible with polyvinyl chloride, forming colorless elastic compounds. The diesters were tested as antioxidants enhancing the thermal oxidation resistance of diesel fuel. The amount of the precipitate formed by oxidative polymerization and polycondensation of diesel fuel due to the presence of heteroatomic compounds decreases from 4.6 to 1.0 mg/100 mL fuel on adding 0.004 wt % diesters prepared.

Synthesis and Study of Mixed Diesters of Synthetic Petroleum Acids and Fatty Acids

Synthesis and Study of Mixed Diesters of Synthetic Petroleum Acids and Fatty Acids

Isosorbide Fatty Acid Diesters Have Synergistic Anti-Inflammatory Effects in Cytokine-Induced Tissue Culture Models of Atopic Dermatitis.

Atopic dermatitis (AD) is a chronic disease in which epidermal barrier disruption triggers Th2-mediated eruption of eczematous lesions. Topical emollients are a cornerstone of chronic management. This study evaluated efficacy of two plant-derived oil derivatives, isosorbide di-(linoleate/oleate) (IDL) and isosorbide dicaprylate (IDC), using AD-like tissue culture models. Treatment of reconstituted human epidermis with cytokine cocktail (IL-4 + IL-13 + TNF-α + IL-31) compromised the epidermal barrier, but this was prevented by co-treatment with IDL and IDC. Cytokine stimulation also dysregulated expression of keratinocyte (KC) differentiation genes whereas treatment with IDC or IDL + IDC up-regulated genes associated with early (but not late) KC differentiation. Although neither IDL nor IDC inhibited Th2 cytokine responses, both compounds repressed TNF-α-induced genes and IDL + IDC led to synergistic down-regulation of inflammatory (IL1B, ITGA5) and neurogenic pruritus (TRPA1) mediators. Treatment of cytokine-stimulated skin explants with IDC decreased lactate dehydrogenase (LDH) secretion by more than 50% (more than observed with cyclosporine) and in vitro LDH activity was inhibited by IDL and IDC. These results demonstrate anti-inflammatory mechanisms of isosorbide fatty acid diesters in AD-like skin models. Our findings highlight the multifunctional potential of plant oil derivatives as topical ingredients and support studies of IDL and IDC as therapeutic candidates.

Two-in-One Surfactant Disinfectant Potential of Xylitol Dicaprylate and Dilaurate Esters Synthesized by Talaromyces thermophilus galactolipase for Cleaning Industries.

Talaromyces thermophilus galactolipase (TTL) was found to produce alcohol sugar fatty acid diesters. The modulation of the solvent composition was used for the esterification reaction screening of diesters from xylitol and various fatty acids using the immobilized Talaromyces thermophilus galactolipase. The reactions were assessed by LC-MS analysis. The antimicrobial activity assay showed that both xylitol dicaprylate and xylitol dilaurate esters had more ability to inhibit the growth of several bacteria involved in surface contamination in the food industry. The xylitol dilaurate ester has the highest activity against Gram-positive strains with the lowest MIC values of 0.0016 and 0.005mgmL-1 against Bacillus licheniformis and Staphylococcus aureus, respectively. Xylitol dicaprylate ester is more active against Gram-negative ones with significantly low MIC values of 0.25 and 0.4mgmL-1 against Escherichia coli and Pseudomonas aeruginosa, respectively. The highest antifungal activity of the xylitol dicaprylate ester has been also proven, with a MIC value of 0.02mgmL-1 against Penicillium occitanis and Fusarium solani. A better reduction in critical micelle concentrations and air-water surface tension were observed with these diesters compared to their corresponding monoesters in addition to their efficient emulsifying properties. The stability of these diesters in a liquid detergent formula after one year of storage was tested by a positive oil spreading assay and a retained antimicrobial activity. They exhibit a typical surfactant behavior with a two-in-one effect that can act as a detergent and a disinfectant with potential use in different cleaning processes.

Improving the performance of diesel engines fuel for agricultural machinery

Quantum-chemical calculations of the parameters of the synthesized molecules have been carried out. There is observed a good correlation of the values of the molecules’ dipole moment and the charge on nitrogen atoms of the investigated compounds with the lubricating properties. Products, containing molecules of long-chain fatty acid diesters obtained from technical camelina oil and triethanolamine, have good lubricating properties.

The anti-Zika virus and anti-tumoral activity of the citrus flavanone lipophilic naringenin-based compounds

Flavonoids are natural products widely recognized for their plurality of applications such as antiviral, antiproliferative, antitumor activities and, antioxidant properties. The flavanone naringenin is presented in citrus fruits and has been studied to combat recurrent diseases that still lack effective treatment. Research groups have been investing efforts to the development of new, safe and active candidates to combat these agents or conditions and despite good results recently reported against the Zika virus (ZIKV) and tumor cells, the use of citrus naringenin is limited due to its low bioavailability. Structural exchanges through functionalization, for example, attaching lipophilic groups instead of hydroxyl groups, can further enhance biological properties.Here, the synthesis and characterization of regioselective naringenin mono-7-O-ethers and both mono and di-fatty acid esters, structurally lipophilic ones were demonstrated. Finally, in vitro studies of anti-ZIKV action and antiproliferative activities against melanoma (B16–F10) and breast carcinoma (4T1) cells showed the ether derivatives were actives, with IC50 ranging from 6.76, 18.5 and 22.6 μM to 28.53, 45.1 and 32.3 μM referring to ZIKV, B16–F10 and 4T1 cell lines, respectively. The lipophilic ethers present the ability to inhibit selectively ZIKV-replication in human cells and inhibitions.This class of modifications in flavonoid molecules could be further explore in the future development of specific anti-ZIKV compounds.

Direct and selective enzymatic synthesis of trehalose unsaturated fatty acid diesters and evaluation of foaming and emulsifying properties

Trehalose diesters are Gemini-type surfactants that might have better surface activity than conventional surfactants. A one-step method for the preparation of trehalose unsaturated fatty acid diesters has been successfully developed. The yield of trehalose diester of different unsaturated fatty acids was between 78 % and 88 % under optimal conditions: 25 mmol/L trehalose, 100 mmol/L unsaturated fatty acid, 60 g/L 3 Å molecular sieves and 20 g/L lipase at 150 rpm and 50 °C for 42 h in 15 mL of acetone. Additionally, trehalose diester was the sole product obtained with Novozym 435 in acetone. The chemical structures of 6,6′-di-O-oleoyltrehalose, 6,6′-di-O-linoleoyltrehalose, 6,6′-di-O-eicosenoyltrehalose and 6,6′-di-O-erucoyltrehalose were confirmed by FTIR, MS and NMR. Moreover, the hydrophile-lipophile balance (HLB) values, foaming properties and emulsifying properties of trehalose diesters were assessed, showing the potentials of these diesters as naturally derived surfactants for the food industry.

Solvent-Free Biocatalytic Synthesis of 2,5-bis-(Hydroxymethyl)Furan Fatty Acid Diesters from Renewable Resources

Fatty acid diesters of 2,5-bis-(hydroxymethyl)furan (BHMF), promising candidates as sustainable bioadditives for increasing the cetane number of biodiesel fuels, were prepared through a solvent-free Novozym 435-mediated diesterification of BHMF with a fatty acid mixture (FAM) resulting from the hydrolysis of commercial sunflower oil. Under solvent-free conditions and a 15 mbar vacuum, high conversions into diesters were obtained in the heterogeneous reaction, after the gradual solubilization of BHMF. After optimization studies (temperature, reaction time, BHMF–FAM ratio, and biocatalyst loading), more than 97% conversion into diesters was achieved. The calculated sustainability metrics support the fact that the currently described solvent-free method represents an improved synthetic procedure for the preparation of BHMF fatty acid diesters.

Effect of chloride on the formation of 3-monochloro-1,2-propanediol fatty acid diesters and glycidol fatty acid esters in fish, meats and acylglycerols during heating

ABSTRACTThe effects of the presence of chloride on the formation of 3-monochloro-1,2-propanediol fatty acid esters (3-MCPDEs) and glycidol fatty acid esters (GEs) in saltwater fish, meats and acylglycerols (diacylglycerol and triacylglycerol) during heating were investigated in this study. Five saltwater fish species (salmon, saury, yellowtail, mackerel and Spanish mackerel) were grilled with a fish griller. 3-MCPDEs and GEs were detected in all of the grilled fish samples. The total amount of GEs was higher than 3-MCPDEs. Beef and pork patties with or without sodium chloride (1.5%) were cooked using gaseous fuel. The formation of 3-MCPDEs was significantly increased by the addition of sodium chloride to the meat patties, whereas the concentration of GEs in the cooked meat patties was not changed by the content of sodium chloride. Hexadecane solutions of diacylglycerol or triacylglycerol containing FeCl3 were heated at 240°C. The formation of 3-MCPDEs was greatly increased by adding FeCl3 to the solutions of triacylglycerol. The amounts of 3-MCPDEs decreased with the extension of the heating time. From these results, it is suggested that 3-MCPDEs and GEs are formed in saltwater fish and meats by cooking, and that the formation of 3-MCPDEs was affected by chloride in foodstuffs.

Eco-Friendly Enzymatic Production of 2,5-Bis(hydroxymethyl)furan Fatty Acid Diesters, Potential Biodiesel Additives

Due to the increasing need for greener and sustainable alternatives to fossil-based industrial chemicals and products, development of efficient synthesis of biomass-based platform chemicals is an attractive goal. 5-Hydroxymethylfurfural (HMF) derived 2,5-bis(hydroxymethyl)furan (BHMF) is one of the most targeted green chemicals, since it is a valuable building block for production of various useful compounds. Herein we described the efficient enzyme catalyzed double esterification of BHMF with saturated long-chain fatty acids using biomass-derived 2-methyl-tetrahydrofuran (2-MTHF) as solvent, providing an efficient synthetic route with >99% overall conversion (BHMF mono- and diesters) and between 89 and 99% conversion into the targeted BHMF diesters. The optimized large-scale procedure yielded easily isolable and chemically pure products useful to improve the cetane number of biodiesel.

Occurrence and exposure of 3-monochloropropanediol diesters in edible oils and oil-based foodstuffs from the Spanish market

During the industrial refining process of edible oils and the manufacture of oil-based foodstuff, contaminants such as 3-monochloropropanediol (3-MCPD) fatty acid diesters can be produced. One hundred samples of different edible oils and related fatty food purchased from local Spanish markets were analyzed to evaluate the occurrence of these contaminants. Data of seven 3-MCPD diesters together with corresponding total 3-MCPD equivalents are presented. The procedure is based on a modified QuEChERS protocol followed by LC-MS/MS analysis. Extra virgin olive oil (EVOO) and unrefined oils did not contain detectable levels of the target analytes. The highest levels of 3-MCPD diesters were found in palm oils, for 1,2-Dilinoleoyl-3-chloropropanediol (LILI) and 1–2-Bispalmitoyl-3-chloropropanediol (PAPA) with concentrations close to 10 mg kg−1 and in the lipid fraction of margarines (8.09, 3.77 and 3.72 mg kg−1 for LILI, PAPA and 1-Oleoyl-2-linoleoyl-3-chloropropanediol (OLLI), respectively).

Development of a partitioned liquid-liquid extraction- dispersive solid phase extraction procedure followed by liquid chromatography-tandem mass spectrometry for analysis of 3-monochloropropane-1,2-diol diesters in edible oils

A fast and effective method using a modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) approach which includes partitioned liquid-liquid extraction (PLLE) and dispersive solid phase extraction (dSPE) clean-up step for the determination of seven 3-monochloropropane-1,2-diol (3-MCPD) fatty acid diesters in vegetable oils is developed and validated according to the Food and Drug Administration (FDA) guidelines. Due to the complexity of the matrices, combination of silica based sorbents (Silica Strong Anion Exchange (Si-SAX), Supel™ QuE Z-Sep+ (Z-Sep+) and Primary Secondary Amine (PSA) were tested for lipid removal. The effect of several experimental factors on the efficiency of the extraction procedure was studied by a screening design 3422//16 and a response surface Doehlert design. The separation and determination was carried out by liquid chromatography coupled with tandem mass spectrometry (LC–MS/MS). The method provided suitable linearity (r2 > 0.9960), precision (relative standard deviation (RSD) lower than 10%) and accuracy, in terms of recovery. The limits of detection (LOD) and limits of quantification (LOQ) ranged from 10 to 20 μg kg −1 and from 25 to 50 μg kg−1, respectively. The recoveries at three spiking levels of 100, 250, and 500 μg kg−1 were over the range of 71.4–122.9% with RSD lower than 13%. The method was successfully applied in edible oils and fatty food samples. The results provide valuable information to assess the risk of exposure to these foodborne contaminants.

Microwave-assisted catalytic esterification of α-glucoisosaccharino-1,4-lactone with tall oil fatty acids

Carbohydrates-rich materials are partly degraded during alkaline kraft pulping into a complex mixture of aliphatic carboxylic acids consisting of α-glucoisosaccharinic acid as one of the main acids. On the other hand, crude tall oil, containing significant amounts fatty acids, is obtained as a by-product from kraft pulping. One interesting novel approach is to utilize chemically both these side-streams by producing renewable surfactants from aliphatic carboxylic acids and fatty acids via esterification. In this paper, lauric (C12:0) and oleic (C18:1) acids as well as a mixture of tall oil fatty acids were esterified with α-glucoisosaccharino-1,4-lactone in a microwave-assisted batch reactor using a respective molar ratio of 3:1 in the presence of p-toluenesulfonic acid as a catalyst to obtain a mixture of the corresponding mono- and diesters (nonionic surfactants) at 70–100 °C for 6–24 h. The total yields varied in the range of 40–62 % and the mass ratio of monoesters to diesters (0.4–2.7) was greatly dependent on the fatty acid feedstock. It seems that relatively high yields of mono- and diesters of typical fatty acids can be obtained when they are esterified with one of the most significant lactones (α-glucoisosaccharino-1,4-lactone) in black liquor from kraft pulping. These esters are potential surfactants based on renewable feedstocks.

Insights into the formation mechanism of chloropropanol fatty acid esters under laboratory-scale deodorization conditions

Chloropropanol fatty acid esters (CPFAEs) are well-known contaminants in refined oils and fats, and several research groups have studied their formation. However, the results obtained in these studies were not satisfactory because the CPFAEs were not analyzed comprehensively. Thus, in the present study, a comprehensive analysis was performed to obtain new details about CPFAE formation. Each lipid (monopalmitin, dipalmitin, tripalmitin, monoolein, diolein, triolein, and crude palm oil) was heated at 250°C for 90min, and the CPFAEs were analyzed using supercritical fluid chromatography/tandem mass spectrometry. It was found that CP fatty acid monoesters were formed from monoacylglycerols and diacylglycerols after heating in the presence of a chlorine compound. In addition, CP fatty acid diesters were formed from diacylglycerols and triacylglycerols under the same conditions. In the case of crude palm oil, only CP fatty acid diesters were formed. Therefore, these results indicated that CPFAEs in refined palm oil were formed mainly from triacylglycerols.

UHPLC-QTOF-MS as a valuable tool for the identification of novel faradiol fatty acid diesters of Calendula officinalis flowers

Calendula officinalis L. (marigold) flower extracts are recommended for the treatment of minor inflammation of the skin and wounds [1]. Triterpenes from the 20-taraxastene type, especially faradiol seem to be crucial for the anti-inflammatory potential [2, 3]. Besides monols triterpene diols and triols are present in the form of their C3 lauric, myristic and palmitic acid monoesters. Here we report on the isolation of a mixture of novel faradiol fatty acid diesters (20-taraxastene 3β,16β-diester). 1D and 2D NMR analysis revealed the triterpene skeleton and the esterification position. However, only after UHPLC-QTOF-MS analysis the fatty acids could be identified and assigned to the respective triterpene. This method allowed identification of intact [M+H+]+ molecular ion peaks of faradioldimyristate (863.7354 m/z), faradioldipalmitate (919.8302 m/z) and faradiolmyristate, palmitate (891.7633 m/z). Moreover, this technique is also suitable for the separation and identification of the arnitriol A 3- and the lupane-3β,16β,20-triol 3-fatty acid monoesters which is here reported for Calendula officinalis L. flowers for the first time.

Study of the carotenoid composition in membrillo, guanabana toreta, jobo and mamey fruits

Introduction. Many tropical fruits have great health potential due to the possible presence of bioactive phytochemicals. Natural food composition databases are very important sources of information relative to natural food biodiversity and nutritional properties. The objective of this study was to report for the first time on the native carotenoid composition of the fruit of four tropical species from Panama. Materials and methods. Fully mature fruit were collected in Panama and analyzed by HPLC-DAD-APCI-MS, after carotenoid extraction with acetone. Results and discussion. The carotenoid composition had never been previously reported for two of the investigated fruits, membrillo (Gustavia superba ) and guanabana toreta (Annona purpurea ). In membrillo, 5 different carotenoids were detected; the content of total carotenoids was 318.6 μ g g-1 fresh weight (fw), with β -carotene showing a relative abundance of 75.3%. In guanabana toreta, 11 different carotenoids were detected; the total carotenoid content was 48.3 μ g g-1 fw, with β -carotene and zeaxanthin showing a relative abundance of 26.9% and 27.5%, respectively. In jobo (Spondias mombin ), 11 different carotenoids were detected; the total carotenoid content was 45.8 μ g g-1 fw, with β -cryptoxanthin, α -carotene and β -carotene showing a relative abundance of 25.4%, 10.5% and 8.5%, respectively. In mamey (Mammea americana ), 16 different carotenoids were detected; the total carotenoid content was 145.2 μ g g-1 fw; in particular, 10 different violaxanthin fatty acid diesters, of both cis and trans isomers, were determined. Conclusion. The consumption of the fruit studied should be promoted both locally and abroad, because of the reported presence of these health-promoting phytochemicals.

Analysis of 1,2-diol diesters in vernix caseosa by high-performance liquid chromatography – atmospheric pressure chemical ionization mass spectrometry

Fatty acid diesters of long-chain 1,2-diols (1,2-DDE), or type II wax diesters, were analyzed in the vernix caseosa of a newborn girl. 1,2-DDE were isolated from the total lipid extract by the semipreparative TLC using plates coated with silica gel. Chromatographic separation of the 1,2-DDE molecular species was achieved on the non-aqueous reversed-phase HPLC with two Nova-Pak C18 columns connected in series (a total length of 45cm) and using an acetonitrile–ethyl acetate gradient. 1,2-DDE eluted from the column in the order of their equivalent chain number. The analytes were detected as ammonium adducts by an ion-trap mass spectrometer equipped with an atmospheric pressure chemical ionization source. Their structures were elucidated using tandem mass spectrometry with MS, MS2 and MS3 steps in a data-dependent mode. More than two thousand molecular species of 1,2-DDE were identified in 141 chromatographic peaks. The most abundant 1,2-DDE were monounsaturated lipids consisting of a C22 diol and a C18:1 fatty acid together with C16:0, C14:0 or C15:0 fatty acids. The positions of double bonds were characterized by the fragmentation of [M+C3H5N]+ formed in the ion source.

Accumulation of astaxanthin by a new Haematococcus pluvialis strain BM1 from the white sea coastal rocks (Russia).

We report on a novel arctic strain BM1 of a carotenogenic chlorophyte from a coastal habitat with harsh environmental conditions (wide variations in solar irradiance, temperature, salinity and nutrient availability) identified as Haematococcus pluvialis Flotow. Increased (25‰) salinity exerted no adverse effect on the growth of the green BM1 cells. Under stressful conditions (high light, nitrogen and phosphorus deprivation), green vegetative cells of H. pluvialis BM1 grown in BG11 medium formed non-motile palmelloid cells and, eventually, hematocysts capable of a massive accumulation of the keto-carotenoid astaxanthin with a high nutraceutical and therapeutic potential. Routinely, astaxanthin was accumulated at the level of 4% of the cell dry weight (DW), reaching, under prolonged stress, 5.5% DW. Astaxanthin was predominantly accumulated in the form of mono- and diesters of fatty acids from C16 and C18 families. The palmelloids and hematocysts were characterized by the formation of red-colored cytoplasmic lipid droplets, increasingly large in size and number. The lipid droplets tended to merge and occupied almost the entire volume of the cell at the advanced stages of stress-induced carotenogenesis. The potential application of the new strain for the production of astaxanthin is discussed in comparison with the H. pluvialis strains currently employed in microalgal biotechnology.

Correction to Free Radical Mediated Formation of 3-Monochloropropanediol (3-MCPD) Fatty Acid Diesters

Correction to Free Radical Mediated Formation of 3-Monochloropropanediol (3-MCPD) Fatty Acid Diesters

HPLC Analysis of Carotenoids from Tomatoes Using Cross-Linked C18 Column and MS Detection

This study was conducted to analyze carotenoids from tomatoes by high-performance liquid chromatography using reversed-phase C18 silica having cross-linked end-capping with diode array and mass spectrometric detection. An efficient gradient elution system was developed to achieve good and reliable separation of both major and minor carotenoids as well as their isomers. Resolution of lycopene, β-carotene and their isomers was 0.91-3.97 and 1.02-2.86 with cross-linked and conventional C18 column, respectively. The % recovery for zeaxanthin, lycopene and β-carotene was found to be in the range of 89-97%. Limits of detection and quantification of 19.44 and 64.79 ng/mL for zeaxanthin, 15.6 and 52.4 ng/mL for lycopene and 8.28 and 27.61 ng/mL for β-carotene were determined. More carotenoid compounds could be separated and detected with the new method as compared with conventional C18 column. Hyphenation of HPLC with photodiode array and mass spectrometry detectors assisted in detection of tetra-dehydrocarotenoid and fatty acid diesters of xanthophylls in tomato products. Content of all-trans-lycopene, β-carotene and total carotenoid in different industrial tomatoes tested was found to range between 41.87 and 84.65, 0.89 and 1.50 and 53.22 and 112.60 µg/g fresh weight, respectively.