- Esterification activity and stability of Talaromyces thermophilus lipase immobilized onto chitosan
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The Talaromyces thermophilus lipase (TTL) was immobilized by different methods namely adsorption, ionic binding and covalent coupling, using various carriers. Chitosan, pre-treated with glutaraldehyde, was selected as the most suitable support material preserving the catalytic activity almost intact and offering maximum immobilization capacity (76% and 91%, respectively). The chitosan-immobilized lipase could be reputably used for ten cycles with more than 80% of its initial hydrolytic activity. Shift in the optimal temperature from 50 to 60 °C and in the pH from 9.5 to 10, were observed for the immobilized lipase when compared to the free enzyme. The catalytic esterification of oleic acid with 1-butanol has been carried out using hexane as organic solvent. A high performance synthesis of 1-butyl oleate was obtained (95% of conversion yield) at 60 °C with a molar ratio of 1:1 oleic acid to butanol and using 100 U (0.2 g) of immobilized lipase. The esterification product is analysed by GC/MS to confirm the conversion percentage calculated by titration.
- Romdhane, Ines Belhaj-Ben,Romdhane, Zamen Ben,Gargouri, Ali,Belghith, Hafedh
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- Two-phase (bio)catalytic reactions in a table-top centrifugal contact separator
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(Figure Presented) A new spin on catalysis: A table-top centrifugal contact separator allows for fast continuous two-phase reactions to be performed by intimately mixing two immiscible phases and then separating them. Such a device has been used to produce biodiesel from sunflower oil and MeOH/NaOMe. A lipase-catalyzed esterification of oleic acid with nBuOH (see picture) also proceeds with high conversion and can be run for up to 13 h.
- Kraai, Gerard N.,Van Zwol, Floris,Schuur, Boelo,Heeres, Hero J.,De Vries, Johannes G.
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- Self-assembled lipase nanosphere templated one-pot biogenic synthesis of silica hollow spheres in ionic liquid [Bmim][PF6]
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The spontaneous self-assembly of hydrophobic enzymatic protein triacylglycerol acylhydrolase (commonly known as lipase and a member of the serine hydrolase family) in hydrophobic 1-butyl-3-methylimidazolium hexafluorophosphate [Bmim][PF6] and in hydrophilic 1-butyl-3-methylimidazolium tetrafluoroborate [Bmim][BF4] ionic liquids resulted in the formation of lipase enzyme nanocapsules of different morphology. The lipase enzyme capsules were found to retain varying enzyme activity in both cases with both kinds of lipase capsules acting as self-catalyzing functional templates for the hydrolysis of silica precursors into silica. The presence of silica and its interaction with biomolecules was proved by X-ray Photoemission Spectroscopy (XPS). Interestingly, hollow silica spheres were obtained in the case of [Bmim][PF6] ionic liquid, while solid silica spheres were obtained in the case of [Bmim][BF4] ionic liquid for the same enzyme. The structural orientation of the enzyme within the capsules, their functional templating to obtain silica particles of varying morphology and finally their combined catalytic activity depend on the initial lipase-ionic liquid interaction. The enzyme activity of all these materials was evaluated against the esterification reaction between oleic acid (fatty acid) and butanol, i.e. biodiesel production. The relative enzyme activity was found to be 93.30% higher in the case of lipase nanocapsules synthesized in [Bmim][PF6] and its in situ templating action to make hollow silica spheres further enhanced the residual activity. Furthermore time dependent kinetics of esterification by hollow silica spheres has also been shown here. Hollow silica spheres can also be used as a reusable catalyst for up to 6 cycles. This work demonstrates that the choice of ionic liquid is critical in controlling the self-assembly of enzymes as the ionic liquid-enzyme interaction plays a major role in retaining capsule activity and enzyme function.
- Sarkar, Sampa,Mantri, Kshudiram,Kumar, Dinesh,Bhargava, Suresh K.,Soni, Sarvesh K.
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p. 105800 - 105809
(2015)
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- Esterification and interesterification reactions catalyzed by acetone powder from germinating rapeseed
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Acetone powder from germinating rape (Brassica napus L.) seedlings exhibits essentially similar activity in lipolysis of triacylglycerols as the corresponding seedling homogenates. Acetone powder from rape seedlings catalyzes the esterification of a fatty acid, such as oleic acid, with n-butanol or a long-chain alcohol, such as oleyl alcohol. Furthermore, the acetone powder catalyzes alcoholysis of a methyl ester, such as methyl oleate with n-butanol or oleyl alcohol, and acidolysis of methyl oleate with a fatty acid, such as erucic acid. However, triacylglycerols are not accepted as substrates for interesterification reactions. In esterification of fatty acids with n-butanol, catalyzed by the acetone powder from rape seedlings, fatty acids having an olefinic bond next to the carboxyl group as a cis-6 double bond, e.g., γ-linolenic, gorlic and petroselinic acids, or those having a cis-4 double bond, e.g., docosahexaenoic acid, are strongly discriminated against as substrates. Such substrate selectivities can be utilized for the enrichment of definite fatty acids from mixtures, derived from naturally occurring oils, via kinetic resolution.
- Jachmanian,Mukherjee
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- Immobilization of Rhizopus oryzae lipase on silica aerogels by adsorption: Comparison with the free enzyme
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Rhizopus oryzae lipase (ROL) was immobilized by physical adsorption onto silica aerogels. The functional properties of immobilized lipase were determined and compared to the soluble lipase ones. The optimum temperature for both free and immobilized lipase activities was 37 °C. We found that the immobilization of R. oryzae lipase onto silica aerogels increased remarkably its stability at high temperatures and within a wade pH range. Besides the immobilized enzyme exhibited a high tolerance to apolar solvent and retained its fully activity in suspension after 4 months of storage at 4 °C. This immobilized biocatalyst is applied in n-butyl oleate synthesis by esterification of oleic acid with n-butanol, using hexane as an organic solvent. The best conversion yield of the ester butyl oleate was obtained with the immobilized lipase (80% versus 35% with the free lipase). This catalytic esterification has been carried on the presence of hexane at 37 °C with oleic acid to butanol molar ratio of 1:1 and 450 IU of immobilized lipase. Furthermore, the reuse of the lipase immobilized by adsorption allowed us to observe that its can achieved 12 successive cycles, without a significant loss of its catalytic activity. Such results revealed good potential for recycling under non-aqueous system.
- Kharrat, Nadia,Ali, Yassine Ben,Marzouk, Sana,Gargouri, Youssef-Talel,Karra-Chaabouni, Maha
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- Chemically Modified Lipase from Thermomyces lanuginosus with Enhanced Esterification and Transesterification Activities
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Lipase from Thermomyces lanuginosus is one of the most explored enzymes for the esterification of several added-value industrial compounds, such as biodiesel, fragrances, and flavors. Its selectivity in these reactions is mostly related with its activity towards small alcohols. In this work, the impact of the chemical modification, with 4 dodecyl chains at its surface, was evaluated regarding its transesterification and esterification activities, comparing with the native form. Linear size-differentiated alcohols (from 1 to 20 carbons in the aliphatic chain) were used to explore for the first time the effect of the chain length in both transesterification and esterification reactions, using p-nitrophenyl palmitate and oleic acid as model compounds, respectively. The chemically modified lipase showed an outstanding improvement of its catalytic performance than the native enzyme, being this increase directly proportional to the size of the alcohols chain used as substrates. The enormous potential and remarkable versatility of this novel super catalyst was here demonstrated, where diverse types of esters, differing in their potential applications (biodiesel, cosmetics, fine chemistry), were efficiently synthesized. The produced esters were fully characterized by 1H NMR, GC-MS, and FTIR.
- Noro, Jennifer,Cavaco-Paulo, Artur,Silva, Carla
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p. 4524 - 4531
(2021/09/02)
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- Method for catalyzed synthesis of butyl oleate with oleic acid-based ionic liquid microemulsion
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The invention discloses a method for catalyzed synthesis of butyl oleate with an oleic acid-based ionic liquid microemulsion. The method comprises the following steps: (1) at 25-35 DEG C, uniformly mixing a surfactant with an imidazole disulfate ionic liquid so as to obtain a surfactant mixed solution, further uniformly mixing with oleic acid and n-butyl alcohol, finally adding an imidazole fluoborate ionic liquid, and stirring so as to obtain an oleic acid-based ionic liquid microemulsion; (2) putting the oleic acid-based ionic liquid microemulsion of the step (1) into a nitrogen atmosphere,heating, stirring to carry out reactions, separating, and purifying, thereby obtaining butyl oleate. The reaction process is gentle in condition, no conventional toxic organic solvent (such as cyclohexane and methylbenzene) except reactants is used, the idea of green and environment protection can be met, the product can be easily separated, and the product is light yellow or golden yellow and ishigh in yield.
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Paragraph 0031-0050
(2019/07/04)
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- Development and Validation of a Novel Free Fatty Acid Butyl Ester Gas Chromatography Method for the Determination of Free Fatty Acids in Dairy Products
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Accurate quantification of free fatty acids in dairy products is important for both product quality control and legislative purposes. In this study, a novel fatty acid butyl ester method was developed, where extracted free fatty acids are converted to butyl esters prior to gas chromatography with flame ionization detection. The method was comprehensively validated to establish linearity (20-700 mg/L; R2 > 0.9964), limits of detection (5-8 mg/L), limits of quantification (15-20 mg/L), accuracy (1.6-5.4% relative error), interday precision (4.4-5.3% relative standard deviation), and intraday precision (0.9-5.6% relative standard deviation) for each individual free fatty acid. A total of 17 dairy samples were analyzed, covering diverse sample matrices, fat content, and degrees of lipolysis. The method was compared to direct on-column injection and fatty acid methyl ester methods and overcomes limitations associated with these methods, such as either column-phase absorption or deterioration, accurate quantification of short-chain free fatty acids, and underestimation of polyunsaturated free fatty acid.
- Mannion, David T.,Furey, Ambrose,Kilcawley, Kieran N.
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p. 499 - 506
(2019/01/08)
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- Evolving the Promiscuity of Elizabethkingia meningoseptica Oleate Hydratase for the Regio- and Stereoselective Hydration of Oleic Acid Derivatives
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The addition of water to non-activated carbon–carbon double bonds catalyzed by fatty acid hydratases (FAHYs) allows for highly regio- and stereoselective oxyfunctionalization of renewable oil feedstock. So far, the applicability of FAHYs has been limited to free fatty acids, mainly owing to the requirement of a carboxylate function for substrate recognition and binding. Herein, we describe for the first time the hydration of oleic acid (OA) derivatives lacking this free carboxylate by the oleate hydratase from Elizabethkingia meningoseptica (OhyA). Molecular docking of OA to the OhyA 3D-structure and a sequence alignment uncovered conserved amino acid residues at the entrance of the substrate channel as target positions for enzyme engineering. Exchange of selected amino acids gave rise to OhyA variants which showed up to an 18-fold improved conversion of OA derivatives, while retaining the excellent regio- and stereoselectivity in the olefin hydration reaction.
- Engleder, Matthias,Strohmeier, Gernot A.,Weber, Hansj?rg,Steinkellner, Georg,Leitner, Erich,Müller, Monika,Mink, Daniel,Schürmann, Martin,Gruber, Karl,Pichler, Harald
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p. 7480 - 7484
(2019/04/27)
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- A method of using waste acid to produce sulfonated oil
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The invention provides a method for using waste acid to produce sulfonated oil. The method includes: after the second-step sulponation reaction during a penetrant BX production process, cooling and standing materials to normal temperature, standing for layering, and separating the waste acid from reaction products; placing the waste acid into a suction filtration barrel for suction filtration to allow a small amount of naphthalene sulfonic acid mixed into the waste acid to be reserved on filter cloth so as to obtain waste acid, namely waste sulfuric acid with sulfuric acid mass concentration of about 80%; using the waste sulfuric acid as sulfonating agent sulfonated oil DAH production to perform sulponation reaction; wherein the mole ratio of the waste sulfuric acid after being converted into sulfuric acid with the mass concentration of 100% to butyl oleate is 1.05-1.1:1. By the method, cost is lowered, resources are utilized, and environments are protected.
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Paragraph 0033-0034; 0040
(2017/07/05)
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- Homogeneous and heterogeneous catalytic (dehydrogenative) oxidation of oleochemical 1,2-diols to α-hydroxyketones
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Herein, the preparation of methyl oleate α-hydroxyketone from the corresponding 1,2-diol was investigated using both homogeneous and heterogeneous systems. Homogeneous conditions using a Pd(OAc)2/neocuproine complex were first developed using oxygen as a sole oxidant under mild conditions (MeOH, 50 °C). Under these conditions, the conversion of diol reached 95%, and α-hydroxyketone was obtained with 97% selectivity. The access to α-hydroxyketone has also been studied by dehydrogenation using a range of heterogeneous catalysts under solvent-free conditions at high temperatures (160-180 °C). Dehydrogenation using activated Ru/C under vacuum provided α-hydroxyketone with 93% conversion and 82% GC yield. The optimized conditions were applied to a range of oleochemical diols, including a vegetable oil derivative, to obtain the corresponding α-hydroxyketones with up to 74% isolated yields.
- Vu, Nam Duc,Guicheret, Boris,Duguet, Nicolas,Métay, Estelle,Lemaire, Marc
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p. 3390 - 3399
(2017/07/28)
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- Revealing the Roles of Subdomains in the Catalytic Behavior of Lipases/Acyltransferases Homologous to CpLIP2 through Rational Design of Chimeric Enzymes
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The lipases/acyltransferases homologous to CpLIP2 of Candida parapsilosis efficiently catalyze acyltransfer reactions in lipid/water media with high water activity (aW>0.9). Two new enzymes of this family, CduLAc from Candida dubliniensis and CalLAc8 from Candida albicans, were characterized. Despite 82 % sequence identity, the two enzymes have significant differences in their catalytic behaviors. In order to understand the roles played by the different subdomains of these proteins (main core, cap and C-terminal flap), chimeric enzymes were designed by rational exchange of cap and C-terminal flap, between CduLAc and CalLAc8. The results show that the cap region plays a significant role in substrate specificity; the main core was found to be the most important part of the protein for acyltransfer ability. Similar exchanges were made with CAL-A from Candida antarctica, but only the C-terminal exchange was successful. Yet, the role of this domain was not clearly elucidated, other than that it is essential for activity.
- Jan, Anne-Hélène,Dubreucq, éric,Subileau, Maeva
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p. 941 - 950
(2017/05/26)
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- POSS-derived solid acid catalysts with excellent hydrophobicity for highly efficient transformations of glycerol
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Novel excellent hydrophobic POSS-derived solid acid catalysts were successfully synthesized through free radical copolymerization of polyhedral oligomeric vinylsilsesquioxanes (POSS) with sodium p-styrene sulfonate (POSS-x-SO3H), and characterized by several physicochemical methods. Green routes toward valorization of glycerol via acetalization with benzaldehyde and esterification of glycerol with acetic acid have been proposed. The as-prepared catalysts showed very high activities and selectivities toward glycerol derivatives within a short reaction time, which were even higher than that of homogeneous H2SO4. The POSS-2-SO3H catalyst was recycled up to five times without any significant loss of activity. The excellent performance of these solid acid catalysts is mostly attributed to the combination of superior hydrophobicity and large specific surface area.
- Leng, Yan,Zhao, Jiwei,Jiang, Pingping,Lu, Dan
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p. 875 - 881
(2016/02/18)
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- Synthesis, characterization and catalytic performance of a novel picolinic acid-12-molybdophosphoric acid hybrid catalyst
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A novel 12-molybdophosphoric acid (HPM)-based complex (H2 PI)2(H 3 O)[PMo12O 40] [Mo2 O5 (H2 O)2 (PI)2 ]?11H2 O (PI-HPM) was prepared by modification with picolinic acid (HPI) and characterized by the methods of Fourier transform infrared (FTIR) spectroscopy, thermogravimetry (TG), X-ray powder and single crystal diffraction. The complex retained the classical Keggin structure of bulk HPM, there were some strong hydrogen bonds existing between the [PMo12 O40 ]3- polyanion, the [Mo2 O5 (H2 O)2 (PI)2 ] coordination moiety, the protonated HPI and the lattice water molecules. Then PI-HPM was employed as heterogeneous catalyst for esterification reaction to evaluate its acid-catalytic activity. The complex exhibited high activity and good durability in reaction mixtures, indicating that it was a promising heterogeneous acid catalyst for esterification that including the conversion of oleic acid to oleates.
- Liu, Lijun,Wang, Honghong,Gong, Shuwen,Lu, Jing,Zhang, Qian
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p. 1007 - 1013
(2016/06/15)
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- Immobilization of a thiol-functionalized ionic liquid onto HKUST-1 through thiol compounds as the chemical bridge
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A novel heterogeneous catalyst [HVIm-(CH2)3SO3H]HSO4@HKUST-1 (IL@HKUST-1), with both Lewis and Br?nsted acid sites, was developed for the esterification of oleic acid with short-chain alcohols. HKUST-1 was chemically modified with ethanedithiol, and the vinyl-containing ionic liquid was then grafted onto the carrier through thiol groups. The catalyst IL@HKUST-1 was characterized by XRD, N2 adsorption-desorption, FT-IR, SEM, TG, elemental analysis, and ICP. The results proved that HKUST-1 had typical microporous structure, and the thiol groups were incorporated into the channels of the carrier. Through the reaction of vinyl and thiol, the ionic liquid was successfully immobilized onto SH-HKUST-1 by chemical covalent bonds. The catalyst was applied in the esterification of oleic acid with ethanol, and the optimal conditions were determined as follows: molar ratio of ethanol to oleic acid 12 : 1, catalyst amount 15 wt% (based on oleic acid), reaction time 4 h, and reaction temperature 90 °C. Under the conditions, the conversion of oleic acid was 92.1%. After 5 times of recycling, there was no significant decrease in conversion, showing a certain stability and good reusability of the catalyst. The catalyst also exhibited high catalytic activity in esterification of oleic acid with other short-chain alcohols.
- Chen, Chong,Wu, Zuowang,Que, Yigen,Li, Bingxue,Guo, Qirui,Li, Zhong,Wang, Lei,Wan, Hui,Guan, Guofeng
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p. 54119 - 54128
(2016/07/06)
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- Novel porous and hydrophobic POSS-ionic liquid polymeric hybrid as highly efficient solid acid catalyst for synthesis of oleate
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A novel porous and hydrophobic Br?nsted acidic solid catalyst (POSS-[VMPS][H2SO4]) was successfully synthesized by copolymerization of polyhedral oligomeric vinylsilsesquioxanes (POSSs) and sulfonic acid-functionalized imidazole ionic liquids. Catalytic tests for the esterification of oleic acid with methanol have shown that this newly obtained polymeric hybrid exhibits very high catalytic activity and selectivity, which was more active or comparable to those of the common solid acid Amberlite-732 and liquid acid H2SO4. Moreover, the catalyst has a good recyclability without significant loss in the activity.
- Lu, Dan,Zhao, Jiwei,Leng, Yan,Jiang, Pingping,Zhang, Chenjun
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- Epoxidized fatty acid ester plasticizer epoxidized fatty acid ester plasticizer and manufacturing method
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Epoxidized fatty acid alkyl ester and methods for making epoxidized fatty acid alkyl ester. The epoxidized fatty acid alkyl ester is prepared from a fatty acid alkyl ester starting material comprising at least one of mono-unsaturated and di-unsaturated fatty acid alkyl ester molecules in a combined amount of at least 85 weight percent. Such epoxidized fatty acid alkyl esters can be employed in plasticizer compositions, either alone or in combination with other plasticizers, such as epoxidized natural oils. Such plasticizers in turn may be used in the formation of polymeric compositions.
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Paragraph 0066
(2017/01/26)
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- The 3D model of the lipase/acyltransferase from Candida parapsilosis, a tool for the elucidation of structural determinants in CAL-A lipase superfamily
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Abstract Because lipids are hydrophobic, the development of efficient bioconversions in aqueous media free of organic solvents is particularly challenging for green oleochemistry. Within this aim, enzymes exhibiting various abilities to catalyze acyltransfer reaction in water/lipid systems have been identified. Among these, CpLIP2 from Candida parapsilosis has been characterized as a lipase/acyltransferase, able to catalyze acyltransfer reactions preferentially to hydrolysis in the presence of particularly low acyl acceptor concentration and high thermodynamic activity of water (aw > 0.9). Lipase/acyltransferases are thus of great interest, being able to produce new esters at concentrations above the thermodynamic equilibrium of hydrolysis/esterification with limited to no release of free fatty acids. Here, we present a 3D model of CpLIP2 based on homologies with crystallographic structures of Pseudozyma antarctica lipase A. Indeed, the two enzymes have 31% of identity in their primary sequence, yielding a same general structure, but different catalytic properties. The quality of the calculated CpLIP2 model was confirmed by several methods. Limited proteolysis confirmed the location of some loops at the surface of the protein 3D model. Directed mutagenesis also supported the structural model constructed on CAL-A template: the functional properties of various mutants were consistent with their structure-based putative involvement in the oxyanion hole, substrate specificity, acyltransfer or hydrolysis catalysis and structural stability. The CpLIP2 3D model, in comparison with CAL-A 3D structure, brings insights for the elucidation and improvement of the structural determinants involved in the exceptional acyltransferase properties of this promising biocatalyst and of homologous enzymes of the same family.
- Subileau, Maeva,Jan, Anne-Hélène,Nozac'h, Hervé,Pérez-Gordo, Marina,Perrier, Véronique,Dubreucq, Eric
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p. 1400 - 1411
(2015/08/03)
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- Heterogenization of ionic liquid based on mesoporous material as magnetically recyclable catalyst for biodiesel production
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To develop green and reusable catalysts for the biodiesel preparation, a novel magnetically separable nanocatalyst was fabricated by covalent bonding of 3-sulfopropyl-1-(3-propyltrimethoxysilane) imidazolium hydrogen sulfate ([SO3H-PIM-TMSP]HSO4) on mesoporous silica modified Fe3O4 nanoparticle. The catalyst possessed uniform core-shell structure with magnetic response core and Br?nsted ionic liquid functionalized mesoporous silica shell. The multifunctional catalyst also exhibited appealing physicochemical features like high specific surface area, mesoporous channel, magnetic response, and fine catalytic activity in esterification of oleic acid with alcohol. Under mind conditions, the conversion of oleic acid was up to 93.5%. The catalyst exhibited recyclable property based on magnetism and the separation of the catalyst would be simply using external magnetic field without obvious mass loss, allowing a clean biodiesel product.
- Wan, Hui,Wu, Zuowang,Chen, Wen,Guan, Guofeng,Cai, Yuan,Chen, Chong,Li, Zhong,Liu, Xiaoqin
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p. 127 - 132
(2015/02/18)
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- Carica papaya by-products as new biocatalysts for the synthesis of oleic acid esters
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Carica papaya lipase is a versatile biocatalyst that is employed for many biotechnological purposes. Its lipase activity was first observed to be tightly linked to the insoluble fraction of latex. Nevertheless, recent studies have shown that this activity is also present in the fruit peel and seeds, suggesting that the lipase activity occurs in other parts of the plant. In the present work, the hydrolytic activity on trioctanoin was determined in various plant by-products, including latex, leafs, petioles, meristems, fruits, and the stem. The most hydrolytic activity was found in the latex (11 U/mL), followed by the petioles (1.7 U/mL). The hydrolytic selectivity was determined using triacetin, tripropionin, tributyrin, and trioctanoin. The enzymes present in the latex showed a higher rate of hydrolysis of tributyrin, while those present in the petioles had a preference for tripropionin, possibly indicating the occurrence of at least two different triacylglycerol hydrolases. Five self-immobilized biocatalysts were obtained: lyophilized latex (LL), lyophilized petioles (LP), bagasse from petioles (BP), and, after a simple cold water washing treatment, treated lyophilized latex (TLL), and treated lyophilized petioles (TLP). This procedure yielded a 5- and 10-fold increase in the latex and petiole activity, respectively, on tributyrin. The selected biocatalysts, TLL and BP, were tested for the synthesis of oleic acid esters (OAE), reaching conversions over 80%. Unexpectedly, only BP preferentially synthesized dodecyl oleate (DO) and showed the highest thermostability. Therefore, BP was further assayed for DO synthesis in a packed bed reactor (PBR), achieving 96% conversion over 40 h. This study shows the great potential of C. papaya by-products, particularly BP, as biocatalysts for the synthesis of OAE.
- Armendáriz-Ruiz, Mariana,Mateos-Díaz, Eduardo,Rodríguez-González, Jorge Alberto,María Camacho-Ruiz, Rosa,Gutiérrez-Mora, Antonia,Sandoval-Fabian, Georgina,Gallegos-Tintoré, Santiago,Mateos-Díaz, Juan Carlos
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p. 216 - 223
(2015/12/23)
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- Esterification of oleic acid in [Bmim]BF4/[Hmim]HSO4 + TX-100/cyclohexane ionic liquid microemulsion
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Esterification of oleic acid was carried out in a 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF4)/Triton X-100 + 1-hexyl-3-methylimidazolium hydrogen sulfate ([Hmim]HSO4)/cyclohexane microemulsion. A pseudo ternary phase diagram of the designed systems was drawn to investigate the phase behavior of the microemulsion, with the surfactant [Hmim]HSO4 acting as a catalyst. The effects of various reaction parameters were explored. The results showed that the maximum yield of lauryl oleate reaches 91.17% and its selectivity reaches 98.55% under optimum reaction conditions. The reaction was carried out with 8 wt% catalyst at 373 K for 6 h. The molar ratios of [Bmim]BF4 to the surfactant and of oleic acid to lauryl alcohol were 0.24 and 0.2, respectively. Comparison reactions between different alcohols and oleic acid were also performed, and the results showed that long alkyl chain alcohols promote the reaction rate. UV-vis absorption spectra demonstrated that the generated water enters the [Bmim]BF4 microdomain of the ionic liquid microemulsions. A possible mechanism of the reaction was also presented. All the results indicate that the [Bmim]BF4/TX-100 + [Hmim]HSO4/cyclohexane microemulsion is a very efficient catalyst system for esterification reactions. This journal is
- Jiang, Dongyu,Chen, Li,Wang, Aili,Yan, Zongcheng
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p. 54427 - 54433
(2015/02/19)
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- Process to prepare a phosphorous containing vegetable oil based lubricant additive
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Chemically-modified triglycerides are prepared by reacting epoxidized triglyceride oils with phosphorus-based acid hydroxide or esters. The phosphorus-containing triglyceride derivatives are of the formula: wherein R1″, R2″ and R3″ are independently selected from C3 to C29 aliphatic fatty acid residues, at least one of which comprising one or both of the derivatized methylene groups of the formula: wherein m is 0, 1 or 2, n is 0 or 1, q is 1, 2 or 3, and R and R′ are independently selected from the group consisting of H, straight, branched or cyclic hydrocarbons and substituted hydrocarbons, and aryl groups. The phosphorus-containing triglyceride derivatives so produced have utility as antiwear/antifriction additives for industrial oils and automotive applications.
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Page/Page column 9; 10; 11
(2014/09/16)
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- Hybrid composites octyl-silica-methacrylate agglomerates as enzyme supports
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The use of immobilized enzymes as catalysts may be limited by particle size which must be larger than the mesh that retains them in the reactor. Octyl-silica (OS) beads of 70 μm average size were agglomerated to obtain hybrid organic-inorganic composites with particle sizes between 100 and 200 μm. The agglomeration process has been achieved by polymerization of methacrylate from glycidyl methacrylate and ethylene dimethacrylate in the presence of silica beads and further functionalization of the composite with octyl groups. Methacrylate content of the composite (20%) is high enough to stick OS beads, and low enough to preserve the advantages of these particles as supports. The properties of the octyl silica particles for lipase immobilization have been very closely reproduced with the octyl-silica-methacrylate (OSM) composite. Enzyme loading of 210 mg lipase per gram of support has been achieved on OSM vs 230 mg/g on OS. Also catalytic activity values are close for both catalysts, OSM-lipase remaining fully active and stable after 15 cycles in acetonitrile.
- Fernández, Oscar,Díaz, Isabel,Torres, Carlos F.,Tobajas, Montserrat,Tejedor, Víctor,Blanco, Rosa M.
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p. 204 - 210
(2013/02/25)
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- Biodiesel synthesis from the esterification of free fatty acids and alcohol catalyzed by long-chain Bronsted acid ionic liquid
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A long-chain Bronsted acid ionic liquid (IL), 3-(N,N- dimethyldodecylammonium)propanesulfonic acid p-toluenesulfonate ([DDPA][Tos]), was prepared and characterized by FT-IR, 1H NMR, 13C NMR, UV/vis and TGA. The H0 (Hammett function) value of the IL was also determined. The IL as catalyst was applied to the catalytic synthesis of biodiesel from free fatty acids (FFAs). The influencing factors, such as the type and amount of catalyst, reaction time, molar ratio of fatty acid to methanol and reaction temperature, were investigated. The results indicated that the long-chain Bronsted acid IL showed high catalytic activity and fair reusability. Esterification was accomplished under the following optimized conditions: molar ratio of alcohols to FFA at 1.5:1, mole fraction of ionic liquid at 10%, 60 °C, and 3 h. The products could be separated from the catalyst system by liquid-liquid biphase separation at room temperature with good yields of 92.5% to 96.5%. The catalyst could be reused nine times after the removal of water and alcohol. Therefore, the long-chain Bronsted acid IL has good potential for the synthesis of biodiesel from low-cost feedstocks such as waste oil and woody plant oils.
- He, Leqin,Qin, Shenjun,Chang, Tao,Sun, Yuzhuang,Gao, Xiaorui
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p. 1102 - 1107
(2013/04/24)
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- Studies on the lipase-catalyzed esterification of alkyl oleates in solvent-free systems
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The alkyl oleates were prepared by esterification of oleic acid with alkyl alcohols catalyzed by the lipase from Candida sp. 99-125 in solvent-free system. The influence of several factors, including enzyme concentration, temperature, molar ratio between oleic acid and alkyl alcohols, the structure of alcohols and water content, was also investigated. The results indicated that the reactions catalyzed by Candida sp. lipase at 20 °C, in the presence of 5% (w/w) lipase, on the molar ratio of 1:1 between oleic acid and alcohols, afforded products in high yield and showed high selectivity to primary alcohols. The enzymatic synthesis gave purer products, compared with the conventional chemical synthesis. The lipase from Candida sp. 99-125 was identified to be an effective catalyst in the esterification of alcohol and oleic acid at low temperature.
- Zhong, Hui,Fang, Zheng,Zou, Baohua,Li, Xin,Ouyang, Pingkai,Guo, Kai
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p. 114 - 117
(2013/05/08)
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- Enzymatic Esterification of Oleic Acid with Aliphatic Alcohols for the Biodiesel Production by Candida antarctica Lipase
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Biodiesel can be obtained by esterification reactions of free fatty acids with enzymatic catalysts (lipases). In this study, the immobilized Candida antarctica lipase was employed in enzymatic esterifications of oleic acid with aliphatic alcohols (methanol, ethanol, n-propanol, n-butanol). Some features that influence the enzymatic esterification reaction, such as amount of biocatalysts, reaction time, hydration level and biocatalyst turnover were evaluated. The products were determined by GC-FID and 1H NMR analyses and these analytical methods were compared. The enzymatic catalyst (C. antarctica lipase) was efficient providing high yields of biodiesel (above 90 %) in less than 24 h to ethanol, n-propanol and n-butanol, whereas for methanol, the enzyme was inactive after ten cycles of reaction. Two new quantitative easy methods were also developed to quantify esters produced by 1H NMR based on the α-CH2 protons of oleic acid and esters. The quantification method used in the enzymatic reactions by 1H NMR showed effective with small differences in comparison with GC-FID analyses. Graphical Abstract: C. antarctica lipase was employed in enzymatic esterifications of oleic acid with aliphatic alcohols (methanol, ethanol, n-propanol, n-butanol) for the biodiesel production. A new method was developed to quantify esters produced (biodiesel) by 1H NMR based on the α-CH2 protons. [Figure not available: see fulltext.]
- Rosset, Isac G.,Cavalheiro, Maria Cecilia H. T.,Assaf, Elisabete M.,Porto, Andre L. M.
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p. 863 - 872
(2013/10/08)
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- Novel and highly efficient SnBr2-catalyzed esterification reactions of fatty acids: The notable anion ligand effect
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In this work, the efficiency of Lewis acid catalysts, SnX2 (X = F-, Cl-, Br-, or -OAc), was investigated on the esterification reactions of fatty acids (i.e., myristic, palmitic, stearic, oleic, linoleic, and linoleic) with different alcohols (i.e., methyl, ethyl, propyl, isopropyl, and butyl alcohol). Tin(II) bromide was the most active catalyst in all reactions studied. We investigated the effects of main reaction parameters, such as catalyst concentration, temperature, and nature of alcohol and fatty acid. The highest activity of SnBr2 catalyst was discussed in terms of its lower activation energy, higher Lewis acid strength, and higher softness of anionic ligand. Finally, the SnBr 2 catalyst can be easily recovered and reused without loss of catalytic activity. Graphical Abstract: Effect of the tin catalyst nature on the oleic acid esterification with ethyl alcohol. [Figure not available: see fulltext.]
- Ferreira, Arthur Batista,Cardoso, Abiney Lemos,Da Silva, Marcio Jose
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p. 1240 - 1246
(2014/01/06)
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- Glycerol acyl-transfer kinetics of a circular permutated Candida antarctica lipase B
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Triacylglycerols containing a high abundance of unusual fatty acids, such as γ-linolenic acid, or novel arylaliphatic acids, such as ferulic acid, are useful in pharmaceutical and cosmeceutical applications. Candida antarctica lipase B (CALB) is quite often used for non-aqueous synthesis, although the wild-type enzyme can be rather slow with bulky and sterically hindered acyl donor substrates. The catalytic performance of a circularly permutated variant of CALB, cp283, with various acyl donors and glycerol was examined. In comparison to wild-type CALB, butyl oleate and ethyl γ-linolenate glycerolysis rates were 2.2- and 4.0-fold greater, respectively. Cp283 showed substrate inhibition by glycerol, which was not the case with the wild-type version. With either ethyl ferulate or vinyl ferulate acyl donors, cp283 matched the performance of wild-type CALB. Changes in active site accessibility resulting from circular permutation led to increased catalytic rates for bulky fatty acid esters but did not overcome the steric hindrance or energetic limitations experienced by arylaliphatic esters.
- Laszlo, Joseph A.,Yu, Ying,Lutz, Stefan,Compton, David L.
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scheme or table
p. 175 - 180
(2012/07/01)
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- An efficient activity ionic liquid-enzyme system for biodiesel production
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The efficient production of biodiesel in hydrophobic ionic liquids using immobilized lipase was demonstrated. The use of ionic liquids containing long alkyl chains on the cation has the important advantage of producing homogeneous systems at the start of the reaction but, when the reaction is complete, a three-phase system is created that allows selective extraction of the products using straightforward separation techniques, while the ionic liquid and the enzyme can be reused. Fifteen ionic liquids based on different alkyl chain length of the methyl imidazolium cation ([C10MIM], [C 12MIM], [C14MIM], [C16MIM] and [C 18MIM]) combined with [BF4], [PF6] or [NTf 2] anions were assayed as reaction media for two immobilized lipases (Candida antarctica lipase B and Pseudomonas fluorescens lipase AK) for biodiesel production. The highest synthetic activity was obtained in [C 16MIM] [NTf2] using Novozym 435 (immobilized Candida antarctica lipase with 245.13 U g-1 IME), its activity being more than three times higher than in a solvent-free system. Additionally, in this IL the fatty acid methyl esters production was 90.29% after 3 h, while in the solvent-free system it was 27.3%. The influence of several reaction parameters, such as temperature, methanol-to-oil molar ratio, alkyl-chain length of the alcohols, IL:substrate volume ratios, amount of enzyme, and oils feedstock were studied and optimized.
- De Diego, Teresa,Manjon, Arturo,Lozano, Pedro,Vaultier, Michel,Iborra, Jose L.
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experimental part
p. 444 - 451
(2011/04/18)
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- Investigation of the catalytic efficiency of a new mesoporous catalyst SnO2/WO3 towards oleic acid esterification
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The synthesis of a new, effective and reusable heterogeneous catalyst, mesoporous SnO2/WO3 (SW) to promote the esterification involving oleic acid and ethanol for the production of ethyl oleate is presented here. The developed mesoporous SnO2/WO3 with surface area of 130 m2/g and pore size of 3.9 nm exhibits up to 90% conversion of oleic acid (for 2 h reaction, at 80 °C) with high yield (~92%) to the ethyl oleate, a product of the esterification reaction of oleic acid. The catalyst exhibits a comparable activity of H2SO4, which is a known catalyst for esterification of organic acids. Kinetic investigation reveals that the experimental data follows a first order dependency on the concentration of the oleic acid and the catalyst. The conversion of oleic acid also has noticeable dependency on the reaction temperatures and different alcohols. Regeneration through heating of the used mesoporous SnO 2/WO3 catalyst at 400 °C for 3 h allows it for reuse without losing of its catalytic activity.
- Sarkar, Arpita,Ghosh, Sudip K.,Pramanik, Panchanan
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experimental part
p. 73 - 79
(2010/11/17)
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- Enzyme-based hybrid macroporous foams as highly efficient biocatalysts obtained through integrative chemistry
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Integrative chemistry-based rational design has been used to synthesize the first lipase [C-CRl]@Glymo-Si(HIPE) and [C-TAl]@Glymo-Si(HIPE) hybrid macrocellular biocatalysts, where immobilization of crude enzymes is optimized, while circumventing the reactants' low kinetic diffusion, by the use of silica macroporous hosts. As a direct consequence, these new hybrid biocatalysts display unprecedented cycling catalysis performance, as demonstrated by the syntheses of butyloleate ester (used as biodiesel lubricant), hydrolysis of linoleic-glycero ester derivatives (end products used for detergent and soap generations), and trans-esterification (reaction involved in the synthesis of low viscosity biodiesel). Considering that the catalytic performances are given in terms of absolute conversion percentage and not just relative enzyme activity, the enzyme@Glymo-Si(HIPE) hybrid macrocellular biocatalysts presented in this study display unprecedented high yield cycling catalysis performances, where turnover numbers (TON) and turnover frequencies (TOF) show promise for real industrial applications. This study can be considered as a milestone for enzyme-based heterogeneous catalyzes, thereby enhancing their competitiveness with the supported-catalysts commonly used in industry, in total agreement with current sustainable development issues. Also, the new macrocellular biocatalysts are well-suited for large-scale industrial production because of their above-mentioned performance characteristics, further enhanced by their monolithic character, which eases the separation of the catalysts from other reaction components.
- Brun,Babeau Garcia,Deleuze,Achard,Sanchez,Durand,Oestreicher,Backov
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experimental part
p. 4555 - 4562
(2011/12/15)
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- Melting points and viscosities of fatty acid esters that are potential targets for engineered oilseed
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Our previous isolation of branched-chain fatty acid (BCFA) methyl esters from lanolin was improved and scaled up. Also, oleate esters of isopropanol, oleyl alcohol and normal alcohols of 1-12 carbons chain lengths were prepared. Esters were made by interesterification with sodium alcoholates and by esterification with Candida antarctica lipase. It proved easier to obtain pure esters by the enzymatic synthesis. Melting points and viscosities over the range of 0-70 °C were determined in order to better identify potential lubricant targets that might be produced by genetically modified oilseed crops. Isopropyl and butyl oleate have melting points of -33 and -32 °C, respectively and viscosities that range from ~17 cp (0 °C) to ~2.5 cp (70 °C). They should have suitable stability for lubricants. BCFA esters had viscosities similar to their straight chain analogs. Viscosities increased with alcohol chain length and decreased with temperature. The dependence of viscosity on temperature was fit with an equation based on Erying's rate equation. Some esters with branched acid or branched alcohol moieties, and some oleate esters might be utilized as biolubricants or biofuels on the basis of their melting points and viscosities.
- Yao, Linxing,Hammond, Earl,Wang, Tong
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- Solvent-free esterification catalyzed by surfactant-combined catalysts at room temperature
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Solvent-free esterifications of various carboxylic acids and alcohols can be catalyzed by surfactant-combined catalysts dodecylbenzene sulfonic acid (DBSA) and copper dodecylbenzene sulfonate (CDBS) in moderate to excellent yield at room temperature. The esterification method has two notable advantages: first, there is no need for any solvent, even water, and secondly, no need for energy, the reaction can proceed smoothly at room temperature. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.
- Gang, Li,Xinzong, Li,Eli, Wumanjiang
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p. 348 - 351
(2008/02/10)
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- Improvement in the gas chromatographic resolution of petroselinate from oleate
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In the extraction of oils from seeds of the genus Coriandrum, GC separations of petroselinate from oleate often gave poor resolution of these two isomers. Oleic and petroselinic acids were esterified with a series of alcohols (methanol, ethanol, 1 propanol, 2-propanol, 2-methyl-1 -propanol, 1 -butanol, 3-methyl1-butanol, and 2-ethyl-1-hexanol). GC resolution of the A6 from the Δ9 and Δ11 octadecenoates was examined for all ester derivatives on a polar phase column. The Δ6 and Δ9 isomers were unresolved as methyl esters; however, the 2-ethyl-1-hexyl esters gave baseline separation of all three isomers under temperature programming conditions. When isothermal conditions were optimized for each ester, separation of these isomers was possible with good resolution values (>89%) for all the alcohols except methanol, which had a partial resolution of 51%. The rates of esterification of all the alcohols were determined for reactions with both oleic acid and triolein using potassium hydroxide as the esterification catalyst. Methanol gave the largest rate constant in both acid and oil esterification reactions with a rate constant 10-fold better than all of the other alcohols. Based on rates of reaction, resolution of petroselinate from oleate, and removal of residual alcohol, the ethyl ester derivative appears to be the best choice for seed oils containing petroselinic acid. Copyright
- Isbell, Terry A.,Green, Lindsay A.,DeKeyser, Stephanie S.,Manthey, Linda K.,Kenar, James A.,Cermak, Steven C.
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p. 429 - 434
(2007/10/03)
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- Synthesis and characterization of oleic succinic anhydrides: Structure-property relations
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Alkenyl succinic anhydrides (ASA) were prepared by an -ene reaction of n-alkyl (C1 to C5) oleates with maleic anhydride. The purified compounds were characterized by FTIR, 1H NMR, and MS analytical methods to elucidate their structures. Their physicochemical properties were systematically studied and found to depend on the length of the alkyl radical. Structure-property relations were established for viscosity, m.p., and density. The combination of a long hydrophobic chain and a highly polar group with density values close to that of water implied good emulsification properties for some of these molecules. Comparison of the thermal properties of alkyl oleates and their respective ASA demonstrated that the grafting of maleic anhydride allowed the synthesis of compounds with very low melting temperatures (less than -60°C) and good stability at high temperatures (greater than 350°C) under both air and helium atmospheres. All these properties suggest a strong potential for application in the biolubricant or surfactant fields. The combined influences of the succinic part and variable ester moieties imply that each ASA molecule has its own characteristics, based on which applications could be developed. Copyright
- Candy, Laure,Vaca-Garcia, Carlos,Borredon, Elisabeth
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p. 271 - 277
(2007/10/03)
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- Charge-remote and charge-proximate fragmentation processes in alkali- cationized fatty acid esters upon high-energy collisional activation. A new mechanistic proposal
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The effect of the metal ion on the high-energy collision-induced dissociation (CID) of alkali metal-cationized n-butyl and methyl ester derivatives of palmitic and oleic acid was examined. The results show that the alkali metal ion has a pronounced effect and does not act as a mere 'spectator' ion with respect to the fragmentation process. While C-H cleavage is a dominant process for [M + Li]+ as well as [M + Na]+ precursor ions, C- C cleavage is also significant for the [M + Na]+ ions. Homolytic mechanisms involving the formation of a transient biradical cation are proposed which enable us to rationalize in a straightforward manner all product ions formed by both charge-remote and charge-proximate fragmentations. The mechanistic proposal is discussed in view of available knowledge on electron impact, CID and related processes. In order to predict how the alkali metal ion could affect the reactivity of the postulated biradical state formed following electronic excitation of the alkali metal-cationized molecules, quantum chemical calculations were performed on methyl and n-butyl acetate as model substances. The decreased spin density at the carbonyl oxygen atom in the biradical state may provide an explanation for the greater tendency towards C-C cleavage reactions of the sodium-cationized fatty acid esters relative to the corresponding lithium complexes.
- Claeys, Magda,Nizigiyimana, Liberata,Van Heuvel, Hilde Den,Vedernikova, Irina,Haemers, Achiel
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p. 631 - 643
(2007/10/03)
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- Synthesis and analysis of the C1-C18 alkyl oleates
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The C1-C18 alkyl oleates were prepared in n-hexane by esterification of oleic acid with either the primary and secondary C1-C6 alcohols or the primary fatty C8-C18 alcohols. The esterification was acid-catalyzed in the presence of p-toluene sulfonic acid (p-TSA) in a pseudo-homogeneous phase, or in the presence of the sulfonic macroporous resin (K2411) in the heterogeneous phase. The purified alkyl oleates were characterized by 13C-NMR. The oleic acid/alkyl oleate mixtures were analyzed by high-performance liquid chromatography (HPLC).
- Vieville, Corinne,Mouloungui, Zephirin,Gaset, Antoine
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p. 101 - 108
(2007/10/02)
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- Synthesis of Fatty Acid Ester by Corynebacterium sp. S-401
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Resting cells and acetone-dried cells of Corynebacterium sp.S-401 catalyzed the fatty acid ester synthesis of various alcohols and fatty acids.These reactions were carried out in phosphate buffer and/or organic solvents.In some cases synthetic reactions of esters in nonpolar solvents, such as n-hexane and benzene, gave better results compared with those obtained in phosphate buffer.
- Seo, Chull Won,Yamada, Yasuhiro,Okada, Hirosuke
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p. 405 - 410
(2007/10/02)
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