The incorporation of n-3 polyunsaturated fatty acids into acylglycerols of borage oil via lipase-catalyzed reactions

The purpose of this work was to add n-3 polyunsaturated fatty acids (PUFA) into the acylglycerols of borage oil. The acidolysis reaction between borage oil and n-3 PUFA was carried out with lipase (Lipozyme IM-60) in organic solvent. The effects of temperature, solvent, and water content on the reaction product were investigated. For the acidolysis reaction between acylglycerols (product of the selective hydrolysis of borage oil, catalyzed by immobilized Candida rugosa lipase) and n-3 PUFA, the total content of n-3 and n-6 PUFA in acylglycerols was 72.8% after a reaction time of 18 h. The contents of γ-linolenic acid, eicosapentaenoic acid, and docosahexaenoic acid were 26.5, 19.8, and 18.1%, respectively. By properly controlling the reaction time, acylglycerols with ca. 70–72% PUFA and a ratio of n-3 PUFA to n-6 PUFA from 0–1.09 can be obtained.     

γ-Linolenic acid concentrates from borage and evening primrose oil fatty acidsvia lipase-catalyzed esterification

γ-Linolenic acid (GLA, all-cis 6,9,12-octadecatrienoic acid) has been enriched from fatty acids of borage (Borago officinalis L.) seed oil to 93% from the initial concentration of 20% by lipase-catalyzed selective esterification of the fatty acids withn-butanol in the presence ofn-hexane as solvent. The immobilized fungal lipase preparation, Lipozyme, used as biocatalyst, preferentially esterified palmitic, stearic, oleic and linoleic acids and discriminated against GLA, which was thus concentrated in the unesterified fatty acids fraction. In the absence of hexane, concentrate containing about 70% GLA was obtained. When the reaction conditions, optimized for borage oil fatty acids, were applied to fatty acids of evening primrose (Oenothera biennis L.) oil, concentrates containing 75% GLA were obtained. From both oils, GLA concentrates were prepared efficiently in short reaction times (1–3 h) at 30–60°C. The process can be applied for the production of GLA concentrates for dietetic purposes.     

Enrichment of γ-linolenic acid from borage oil via lipase-catalyzed reactions

Three lipase-catalyzed reactions were utilized to enrich γ-linolenic acid in borage oil: (i) selective hydrolysis in isooctane by Candida rugosa lipase immobilized on microporous polypropylene, (ii) selective esterification of free fatty acid from saponified borage oil and n-butanol by Lipozyme IM-20, and (iii) acidolysis of the products of the previous two reactions, that is, unhydrolyzed acylglycerols and unesterified free fatty acid. In the selective hydrolysis, γ-linolenic acid content could be raised from 23.6 mol% in borage oil to 51.7% in the unhydrolyzed acylglycerols. On the other hand, γ-linolenic acid content in free fatty acid could be increased to 87% after selective esterification. Products with 65% γ-linolenic acid in their acylglycerols were obtained by means of the acidolysis reaction.     

Development of linseed oil based polyesteramide without organic solvent at lower temperature

Linseed oil based polyesteramide was synthesized at lower temperature in the absence of organic solvent through condensation polymerization reaction [Sf‐LPEA]. In this reaction N,N‐bis(2‐hydroxyethyl) linseed oil fatty amide and phthalic anhydride were heated at temperature lower than their onset of melting points and the by‐product, such as water was removed by application of vacuum technique. This approach was employed to overcome the use of volatile organic solvents used during processing and application of resin, which are ecologically harmful. The solubility of Sf‐LPEA was checked in different polar and nonpolar solvents. The FTIR, ¹H NMR, and ¹³C NMR spectral techniques were used to confirm the structure of Sf‐LPEA. The physicochemical, physicomechanical, and chemical resistance properties of the resin were investigated by standard methods. DSC and TGA were used to determine, respectively, the curing behavior and thermal stability of the resin. The comparative study of these properties of Sf‐LPEA with reported polyesteramide [LPEA], which are normally synthesized at higher temperature in organic solvent, was done. It was found that Sf‐LPEA exhibited improved physicomechanical, chemical resistance properties, and higher thermal stability compared with LPEA, and hence can find application as corrosion protective coating. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1143–1148, 2007     

Enzymatic incorporation of docosahexaenoic acid into borage oil

Lipase-catalyzed acidolysis of acylglycerols of borage (Borago officinalis L.) oil with a docosahexaenoic acid (DHA) concentrate, prepared from algal oil, in organic solvents was studied. Seven lipases were used as biocatalysts for the acidolysis reaction. Novozyme 435 from Candida antarctica, as compared to lipases from Mucor miehei and Pseudomonas sp., showed the highest degree of DHA incorporation into borage oil. Other lipases tested, such as those from Aspergillus niger, C. rugosa, Thermomyces lanuginousus and Achromobacter lunatus, were rather ineffective in the incorporation of DHA into borage oil. Effects of variation of reaction parameters, namely, enzyme load, temperature, time course, and type of solvent, were monitored for C. antarctica as the biocatalyst of choice. Incorporation of DHA increased with increasing amount of enzyme, reaching 27.4% at an enzyme concentration of 150 lipase activity units. As incubation time progressed, DHA incorporation also increased. After a reaction time of 24 h, the contents of total n-6 and n-3 polyunsaturated fatty acids in acylglycerols were 44.0 and 27.6%, respectively. The highest degree of DHA incorporation was achieved when hexane was used as the reaction medium. The positional distribution of DHA in modified borage oil was determined using pancreatic lipase hydrolysis. Results showed that DHA was randomly distributed over the sn-1, sn-2, and sn-3 positions of the triacylglycerol. Thus, preparation of modified borage oil acylglycerols containing both DHA (22:6n-3; 27.4%) and γ-linolenic acid (18:3n-6; 17.0%) was successfully achieved and products so obtained may have beneficial effects beyond simple physical mixtures of the two oils. The final oil had a ratio of n-3 to n-6 of 0.42–0.62 which is nutritionally more suitable than the original unaltered borage oil.     

Miscibility studies on linseed oil epoxy blend with poly(methacrylic acid)

With the aim to utilize a vegetable oil epoxy, a product from a sustainable resource, for improving the properties of polymethacrylic acid (PMAA), the blends of the latter with the epoxy of linseed oil were prepared in solution by mechanical mixing of the requisite amounts of the two components in dimethylsulphoxide. Freestanding films of the blend were cast. The miscibility of the two components was investigated by viscosity, ultrasonic, and density measurements which showed that the two components were semicompatible in solution. The compatibility in solid phase was also examined by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM), which revealed that linseed oil epoxy (LOE) and PMAA were incompatible. The films of blend of all compositions were found to be sticky, which was caused by the oozing of LOE. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

亚麻油改性特-辛基酚醛树脂的合成及性能研究

利用亚麻油与松香对辛基酚醛树脂进行改性合成改性辛基酚醛树脂。对改性产品进行了GPC、FT-IR的表征分析及其软化点、脂肪烃溶解性和溶剂溶解性能等的研究。实验表明,亚麻油与松香质量比在20%~40%之间时,所得产品分子量(Mn)6 000~10 000,分子量分布范围(PD I)小于4,庚烷容纳度在10~20 mL/2 g,软化点大于110℃,是平版印刷油墨用的一种新型高分子聚合物。     

Miscibility behavior of blend of polyesteramides of linseed oil and dehydrated castor oil with poly(methacrylic acid)

Blending of two polymers in solution is a simple and cost‐effective technique to improve upon the physical and mechanical properties of the component polymers through synergism. To obtain maximum synergy in their properties, the component polymers should be miscible with each other on molecular scale. Polymer blends of complex physicomechanical properties are being actively investigated. Poly(methacrylic acid) (PMAA), a commercial polymer, yields transparent, hard, brittle, and water‐sensitive films. It has been blended with natural polymers like dextran, collagen, and gelatin to obtain films with improved physical and mechanical characteristics. Polyesteramides, which are easily synthesized from vegetable seeds oil, a sustainable resource, have found application in surface coatings. These oligomeric products do not make free standing films in the ambient condition. The polyesteramides from vegetable seeds oil can be used to obtain blend with PMMA of improved mechanical and water absorption properties. In this study, linseed oil polyesteramide (LOPEA) and dehydrated castor oil polyesteramide (DCPEA), the source oils with different unsaturation in their fatty acid chains, were blended with PMAA through mixing in solution in the ratio DCPEA/LOPEA: PMAA as 80/20, 70/30, 60/40, 50/50, 40/60, 30/70, and 20/80. In the first instance, the miscibility of the two components was investigated in solution by viscosity and ultrasonic measurements and in solid phase through differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Moisture absorption by the blend was also studied. DCPEA and LOPEA show immiscibility with PMAA in solution phase while LOPEA with more unsaturation in the fatty acid chain of the oil was found more immiscible than DCPEA. DCPEA shows a narrow miscibility window in the solid phase while LOPEA was found immiscible with PMAA in the solid phase too. Uptake of moisture was found to be markedly reduced in the blends of DCPEA/LOPEA with PMAA. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1367–1374, 2007:     

The decomposition of secondary esters of castor oil with fatty acids

In this study, thermal splitting of secondary fatty acid esters of castor oil was investigated to determine the reaction kinetics under various conditions. Zinc oxide,p toluenesulfonic acid and sulfuric acid were used as catalysts. Reactions were carried out at 260, 270, and 280°C. Experimental data fitted the first-order rate equation for the catalyzed and noncatalyzed reactions. In addition to the kinetic investigation, the splitting (pyrolysis) mixture was evaluated in the preparation of a synthetic drying oil. For this purpose, the mixed fatty acids of linseed, sunflower andEcballium elaterium seed oils were used in the esterification stage of the process. Pyrolysis mixtures were converted to drying oils by combining the liberated acids with equivalent amounts of glycerol. The oils thus obtained show good drying oil properties.     

Effects of tocopherols and their mixtures on the oxidative stability of olive oil and linseed oil under heating

The tested tocopherols (γ,δ,α) showed antioxidative activity at all levels of addition to the monounsaturated olive oil, the effects increased as a function of concentrations (maximum: +287% with 800 mg γ‐tocopherol/100 g oil compared to the control oil). In the highly unsaturated linseed oil, which contains 58 mg/100 g initial concentration of γ‐tocopherol, γ‐tocopherol showed antioxidative behavior up to the addition of 100 mg/ 100 g oil. Additions of more than the 100 mg/100 g affected the oil, resulting in a faster oxidation. Mixtures of γ/δ‐tocopherols in olive oil were found to protect more efficiently than both vitamins when added separately α‐tocopherol reduced effects of other tocopherols in both plant oils. The stabilizing effect of added tocopherols and their mixtures (100 mg/100 g oil each) in olive oil are γ/δ‐T>γ‐T>δ‐T>γ/α‐T>δ/α‐T>α‐T and in linseed oil γ‐T>γ/δ‐T>δ‐T>γ/α‐T>α‐T>α/δ‐T.     

Synthesis and characterization of low viscous and highly acrylated epoxidized methyl ester based green adhesives derived from linseed oil

Both epoxidized linseed oil and transesterified epoxidized linseed oil were acrylated to form UV curable bio-based oligomers. The synthesis was confirmed by FTIR and ¹H NMR and oxirane oxygen content (OOC). The OOC value of epoxidized linseed oil was determined to be 8.2 % which was reduced to 8.0 % after transesterification confirming the retaining of epoxy groups. The lower OOC of acrylated epoxidized linseed oil (AELO) (2.1 %) and acrylated epoxy methyl esters (AEME) (0.9 %) revealed successful acrylation. The degree of acrylation in AEME was higher (~ 90 %) than AELO (~ 77%) and most importantly, the viscosity of AEME was much lower than AELO revealing better processability for industrial use.     

Synthesis and characterization of poly(esteramide‐urethane) from linseed oil as anticorrosive coatings

Ethylene diamine polyesteramide (Ed‐PEA) was synthesized from N, N‐bis (2‐hydroxy ethyl) linseed oil fattyamide and ethylene diamine tetra acetic acid through condensation polymerization. It was further treated with toluylene 2,4‐diisocyanate (TDI) in different weight percentage to obtain urethane‐modified polyesteramide (Ed‐UPEA). The structural elucidation of Ed‐PEA and Ed‐UPEA were carried out by FTIR, ¹H‐NMR, and ¹³C‐NMR spectroscopic techniques. Thermal studies of these resins were carried by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The coatings of urethane‐modified polyesteramide were prepared on mild steel strips and their anticorrosive behavior of in acid, alkali, water, and xylene were investigated. Thermal stability performance suggests that the system could be safely used upto 200°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Aging study of linseed oil resin/styrene thermosets and their composites with wood flour

The changes in the properties of new crosslinked polymers based on renewable resources and their derived composites have been monitored as a function of time; this knowledge being necessary to estimate their behavior in final applications. Rigid thermoset polymers prepared by free radical polymerization of resins obtained from linseed oil and styrene and composites reinforced with wood flour were evaluated in different environmental conditions and at different times after their preparation. The action of atmospheric oxygen on the unsaturated groups in fatty acids produces chemical changes in these polymers, which affect the properties of the cured materials. These changes were analyzed using Fourier transform infrared spectroscopy, dynamic mechanical analysis and mechanical testing. An increase in the modulus with time was observed during exposure of the samples to dry conditions, or humid environments (60% relative humidity), with or without UV irradiation. The reaction with oxygen appears to be accelerated when the materials are subjected to UV irradiation, showing a large effect on the glass transition temperature. Copyright © 2007 Society of Chemical Industry     

Enrichment of γ-linolenic acid from evening primrose oil and borage oilvia lipase-catalyzed hydrolysis

Lipase-catalyzed selective partial hydrolysis of evening primrose (Oenothera biennis L.) seed oil and borage (Borago officinalis L.) seed oil led to an increase in the level of γ-linolenic acid (GLA; 18∶3n−6) in the unhydrolyzed acylglycerols. Thus, in evening primrose oil, the GLA level could be raised from 9.4% in the starting material to 46.5% in the unhydrolyzed acylglycerols by means of a lipase fromCandida cylindracea. Selective hydrolysis of borage oil with Pancreatin led to an increase in the GLA content from 20.4% in the oil to 33.5% in the unhydrolyzed acylglycerols. Partial hydrolysis of borage oil with lipase fromC. cylindracea raised the GLA content of the acylglycerols to 47.8%.     

Fatty acid selectivity of lipases: γ-linolenic acid from borage oil

The γ-linolenic acid (Z,Z,Z-6,9,12-octadecatrienoic acid, GLA) present in borage oil free fatty acids was concentrated in esterification reactions that were catalyzed by several preparations of the acyl-specific lipase ofGeotrichum candidum. In this manner, a 95% recovery of the GLA originally present in borage oil (25% GLA) was obtained as a highly enriched fatty acid fraction with a GLA content of >70%. Other fatty acids concentrated in this fraction were the monounsaturated fatty acids with chainlengths of C-20 and longer that were present in the oil. An immobilized preparation ofG. candidum on silica gel also was used for the enrichment of GLA in borage oil. In this instance, a 75% recovery of GLA was obtained, and the supported lipase was reusable (three cycles) with minimal loss in activity. Presented in part at the 84th Annual Meeting of the American Oil Chemists’ Society, Anaheim, California, May 1993.     

PMMA‐multigraft copolymers derived from linseed oil,soybean oil,and linoleic acid: Protein adsorption and bacterial adherence

Synthesis of Poly(methyl methacrylate), PMMA‐multigraft copolymers derived from linseed oil, soybean oil, and linoleic acid PMMA‐g‐polymeric oil/oily acid‐g‐poly(3‐hydroxy alkanoate) (PHA), and their protein adsorption and bacterial adherence have been described. Polymeric oil/oily acid peroxides [polymeric soybean oil peroxide (PSB), polymeric linseed oil peroxide (PLO), and polymeric linoleic acid peroxide (PLina)] initiated the copolymerization of MMA and unsaturated PHA‐soya to yield PMMA–PLO–PHA, PMMA–PSB–PHA, and PMMA–PLina–PHA multigraft copolymers. PMMA–PLina–PHA multigraft copolymers were completely soluble while PMMA–PSB–PHA and PMMA–PLO–PHA multigraft copolymers were partially crosslinked. Crosslinked parts of the PLO‐ and PSB‐multigraft copolymers were isolated by the sol gel analysis and characterized by swelling measurements in CHCl₃. Soluble part of the PLO‐ and PSB‐multigraft copolymers and completely soluble PLina‐multigraft copolymers were obtained and characterized by spectroscopic, thermal, gel permeation chromatography (GPC), and scanning electron microscopy (SEM) techniques. In the mechanical properties of the PHA–PLina–PMMA, the elongation at break is reduced up to ～ 9%, more or less preserving the high stress values at its break point (48%) when compared to PLina‐g‐PMMA. The solvent casting film surfaces were studied by means of adsorption of blood proteins and bacterial adhesion. Insertion of the PHA into the multigraft copolymers caused the dramatic increase in bacterial adhesion on the polymer surfaces. PHA insertion into the graft copolymers also increased the protein adsorption. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

双液相萃取棉籽油制备脂肪酸甲酯

以双液相萃取技术处理棉籽,在得到脱毒棉粕的同时得到含有高质量毛油的非极性相。以非极性相作为与甲醇进行酯交换反应的原料,得到脂肪酸甲酯和甘油。考察了非极性相溶剂石油醚与棉籽油的比例对酯交换转化率和洗涤粗产品用水量的影响,确定了石油醚与棉籽油的最佳质量比为3,在此条件下,洗涤用水量可降低一半。考察了醇油比、催化剂用量、反应温度、反应时间等参数对转化率的影响。应用正交实验的方法找出酯交换反应的适宜条件为：醇油比6：1,催化剂用量1.1％,反应温度60℃,反应时间120min。在此反应条件下,产物中脂肪酸甲酯的含量可达97.4％。     

A note on improved isolation of concentrates of linolenic acid and ethyl linolenate from linseed oil

Summary Linolenic acid and ethyl linolenate concentrates (80–85%) have been obtained from linseed oil fatty acids or ethyl esters in 50–60% yield, based on linolenic recovery, by a single urea complex separation at room temperature. This note is IV in the series, “Application of Urea Complexes in the Purification of Fatty Acids, Esters, and Alcohols.” Paper III is reference 6. A laboratory of the Eastern Utilization Research Branch, Agricultural Research Service, U. S. Department of Agriculture.     

Esterification of glycerol with conjugated linoleic acid and long-chain fatty acids from fish oil

Free fatty acids from fish oil were prepared by saponification of menhaden oil. The resulting mixture of fatty acids contained ca. 15% eicosapentaenoic acid (EPA) and 10% docosahexaenoic acid (DHA), together with other saturated and monounsaturated fatty acids. Four commercial lipases (PS from Pseudomonas cepacia, G from Penicillium camemberti, L2 from Candida antarctica fraction B, and L9 from Mucor miehei) were tested for their ability to catalyze the esterification of glycerol with a mixture of free fatty acids derived from saponified menhaden oil, to which 20% (w/w) conjugated linoleic acid had been added. The mixtures were incubated at 40°C for 48h. The ultimate extent of the esterification reaction (60%) was similar for three of the four lipases studied. Lipase PS produced triacylglycerols at the fastest rate. Lipase G differed from the other three lipases in terms of effecting a much slower reaction rate. In addition, the rate of incorporation of omega-3 fatty acids when mediated by lipase G was slower than the rates of incorporation of other fatty acids present in the reaction mixture. With respect to fatty acid specificities, lipases PS and L9 showed appreciable discrimination against esterification of EPA and DHA, respectively, while lipase L2 exhibited similar activity for all fatty acids present in the reaction mixture. The positional distribution of the various fatty acids between the sn-1,3 and sn-2 positions on the glycerol backbone was also determined.     

UV exposure and temperature effects on curing mechanisms in thin linseed oil films: Spectroscopic and chromatographic studies

The influence of thermal and photochemical treatment in the curing mechanisms of thin linseed oil films is studied. The role of copper acetate pigments is also investigated under the above conditions. UV and FTIR absorption spectroscopy and chromatographic product analysis are used as the main analytical techniques, which allowed the identification of significant changes in the curing mechanism in each case. Yellowing, crosslinking, and fragmentation inside the film material proceed to a different extent according to the conditions. Peroxide destruction is induced by UV exposure at early curing stages and affects the course of the yellowing process. Yellow product formation is also favored by curing at elevated temperatures, which is accompanied in this case by decreased crosslinking in the cured film. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 936–949, 2002; DOI 10.1002/app.10117