Characterization of triglycerides isolated from jojoba oil

Triglyceride compounds isolated from jojoba seed oil by column chromatography were composed predominantly of C_18′ C_20′ C_22′ and C₂₄ n−9 fatty acids with minor amounts of saturated C₁₆. Chain length and double-bond positions were determined by gas-liquid chromatography and gas-liquid chromatography-mass spectrometry of the corresponding methyl ester and picolinyl ester derivatives. Triglyceride structures were analyzed directly by ion trap mass spectrometry. The analysis of minor compounds, can provide highly specific information about the identity of an oil.     

Optimisation of the synthesis of an analogue of jojoba oil using a fully central composite design

The development and optimisation of the synthesis of an analogue of jojoba oil has been carried out. The product is an ester with characteristics similar to those of sperm whale oil and jojoba oil. This permits its use as a substitute for these two natural oils. A central composite design has been used in the synthesis of this fine chemical. The variables selected for the present study are reaction temperature, initial concentration of catalyst and working pressure. Temperature is the most significant factor in the esterification process, and its influence is positive. Pressure has a negative influence, and the concentration of catalyst a positive influence, on the process. Depending on the temperature value, the influence of the interactions can be more important than that of the other two main effects, pressure and catalyst concentration. Response surface models have been found adequately to represent the yield of ester. The commercial quality of the synthesised product is very similar to that of natural jojoba oil. Because of its low cost, this synthesis process is considered, from an economical point of view, very attractive.     

Functionalization at the double-bond region of jojoba oil. 8. Chemical binding of jojoba liquid wax to a polymer matrixvia an amine “spacer”

Jojoba wax was chemically bonded to a polymer matrixvia stable C-N covalent bonds. The polymer matrix was prepared by amination of several types of styrene-divinyl benzene or styrene-vinylbenzylchloride-divinylbenzene copolymers with diamines or polyethylene imines (polyamines). The jojoba wax was attached to the aminated polystyrene matrix by reacting an allyl-brominated derivative of jojoba with the matrix to form a C-N bond between the matrix and the jojoba wax. The amount of bound jojoba wax added to the polymer was in the range of 20–70% (w/w), depending on the type of polymer matrix and reaction conditions. The double-bond regions in the jojoba wax bonded to the matrix were preserved, and they were subsequently functionalized by phosphonation and sulfur-chlorination reactions.     

Functionalization at the double-bond region of jojoba oil. 7. Chemical binding of jojoba liquid wax to polystyrene resins

Jojoba wax was chemically bonded to a polystyrene matrixvia a stable C-C covalent bond. This was achieved by binding allyl-brominated jojoba derivatives to lithiated crosslinked polystyrene-2% divinylbenzene or XAD-4 polymeric beads via a nucleophilic substitution reaction. The double-bond regions in the jojoba wax were preserved. A side reaction that accompanied the nucleophilic substitution was HBr elimination, which produced diene and triene systems in the bound jojoba. Phosphonation and sulfur chlorination at the double bonds of the jojoba wax, bonded to the polystyrene matrix, were also performed.     

Functionalization at the double-bond region of jojoba oil. 9. solid-state nuclear magnetic resonance characterization of substituted jojoba wax chemically bonded to a polystyrene matrix

Solid extractants for metal ions have been prepared by chemical bonding of jojoba wax to a polystyrene backbone, followed by phosphonation or sulfur-chlorination of the jojoba moiety. In this study, the intermediates and final solid products of the reactions were characterized by solid-state ¹³C and ³¹P nuclear magnetic resonance spectroscopy. The spectra showed the expected chemical shifts of the atoms involved in the chemical reactions, as well as other parts of the reacting molecules. Thus, the carbonyl carbon of the jojoba chain appears at 175 ppm, the methyl carbons at 15 ppm, the polystyrene backbone at 40–42 ppm (aliphatic carbons) and 128, 137, 143–147 (aromatic carbons). Carbons adjacent to N, S, and P appear at 45–55, 60, and 48 ppm, respectively.     

An efficient synthesis of muscalure from jojoba oil or oleyl alcohol

A four-step synthesis of (Z)-9-tricosene (muscalure), a component of the pheromone of the housefly, from jojoba oil (or three-step from oleyl alcohol) by 3-carbon (or 5-carbon) unit elongation was developed in overall high yield. The sequence of reactions and the purity of the products could be easily followed, with relatively good accuracy, by NMR technique.     

A wet process technology applied to jojoba seed to obtain oil and detoxified protein meal

An industrial wet process to obtain oil and meal from jo-joba was set up. The process sequence consists of breaking the seeds, homogenizing with water of suitable pH and temperature, and centrifuging to accomplish separation into oil, process water and wet meal. Oil is obtained with a yield of 70–75% and requires no supplementary refining treatment for the industrial purposes for which it is destined. The meal obtained is devoid of the toxic components simmondsin and simmondsin-2′ ferulate, and the protein content may be considered unchanged. The procedure contemplates a drying treatment for the meal with a view to using it as animal feed. This system is simple, economical and flexible in use.     

Chemical binding of jojoba liquid wax to polyethylene

Jojoba wax was chemically bonded to polyethylene—in film or hollow fiber form—via a stable sulfonamide bond. The jojoba-bonded polyethylene was obtained by binding allyl amino jojoba derivatives to chlorosulfonated polyethylene. The amount of jojoba added to the polymer ranged from 9 to 98% (w/w), depending onthe reaction conditions. Swelling of the polymer in the reaction solvent was the major factor affecting the efficacy of the chemical binding of the jojoba amino groups to the chlorosulfonyl entities of the polymer. The double-bond regions in the bound jojoba wax were preserved, i.e., they were shown to be reactive in a bromination reaction. These modified membranes can find application in separation processes, such as metal ion separation and pervaporation.     

Pinacol rearrangement of jojoba bis-epoxide

Jojoba bis-epoxide (1.6 mmol) undergoes pinacol rearrangement upon reaction with the iodide ion (60 mmol) under slightly acidic conditions, via an iodohydrin as an intermediate, to yield bis-ketojojoba in high yield (92%) after 25 h reflux in THF; no hydroxy derivatives were detected. Since the nucleophilic opening of the epoxide ring is statistically equal on both sides, the rearranged product may have the two carbonyl groups on either side of the original carbon atoms of the two epoxide rings, both completely opened. MS of the rearranged products reveals that the ring opening is approximately equal on both sides of the epoxide ring. Other nucleophiles, such as acetate and amine, open the ring sluggishly without rearrangement.     

Composition and oxidative stability of soybean oil in mixtures with jojoba oil

Improvement of the oxidative stability of soybean oil (SBO) by blending with jojoba oil (JO) was investigated. SBO in the presence of 5, 10, 15 and 20 wt‐% of JO was subjected to accelerated storage at 60 °C. Peroxide values (PV), anisidine values (AV), UV absorption characteristics (K₂₃₂ and K₂₇₀ values), and headspace volatiles were determined to monitor the oxidative stability of oil samples. JO was effective in reducing the formation of hydroperoxides and volatile compounds in SBO. The effect was remarkable in SBO/JO blends containing 15 and 20% JO, which showed significant reductions in PV, AV and volatile content with respect to pure SBO. The increased oxidative stability of SBO/JO blends could not be attributed to JO tocopherols, since the addition of JO to SBO significantly reduced the tocopherol content of SBO. Besides the tocopherol content and unsaturation degree of SBO and JO, the effect of the JO ester structure on the oxidative stability of the blends is discussed. The enhanced chemical and flavor stabilities of SBO/JO blends with respect to pure SBO may make a significant contribution to improve the shelf life of SBO by reducing the deterioration reactions related to lipid peroxidation.     

Solubilization of lycopene in jojoba oil microemulsion

The unique properties of jojoba oil make it an essential raw material in the manufacture of cosmetics. New, totally dilutable U-type microemulsions of water, jojoba oil, alcohols, and the nonionic surfactant polyoxyethylene-10EO-oleyl alcohol (Brij 96V) have been formulated recently. Here, these microemulsions are shown to be capable of solubilizing lycopene, a nutraceutical insoluble in water and/or oil, much more effectively than the solvent (or a solvent and surfactant blend) can dissolve them. In water-in-oil (W/O) and oil-in-water (O/W) microemulsions with 10 and 90 wt% water, respectively, the normalized maximal solubilization efficiency α is ca. 20-fold larger than its solubility. The solubilization capacity of the system is mainly surfactant-concentration dependent. The lycopene resides at the interfaces of the W/O and O/W microemulsions and engenders significant structural changes in the organization of the microemulsion droplets. In the absence of lycopene, the droplets are spherical; when lycopene is added, compaction of the droplets and formation of threadlike droplets are observed. On further addition of lycopene, the bridging effect wanes and the droplets revert to a spherical shape. The enhanced solubilization demonstrated for lycopene opens up new options for formulators interested in making liquid and transparent products for cosmetic or pharmaceutical uses.     

Lipase-mediated synthesis of dodecyl oleate and oleyl oleate in aqueous foams

Engineering media for optimal product yield in enzyme-catalyzed reactions is an important strategy. We report here synthesis of dodecyl oleate and oleyl oleate by lipase (Candida rugosa) in solvent-free substrate foams. Ester formation was characterized with respect to enzyme concentration, pH, temperature, and substrate concentration. The kinetics of ester formation suggest that the formation of ester was 80% complete in 2h. The pH and temperature optima of lipase suggest that the behavior of lipase in substrate foams was similar to its behavior in water or in organic solvents. The denaturing effect of foams on enzyme was evaluated. Rapid loss in activity (>70% in 1 h) was observed in the presence of oleic acid and dodecanol. The large surface areas generated in aqueous foams offer better accessibility of substrate to lipase for esterification.     

Functionalization at the double bond region of jojoba oil. 6. Production of aminesvia azides

The apolar and hydrophobic jojoba molecule was made more hydrophilic by the incorporation of primary amino groupsvia the introduction and subsequent reduction of azido groups. The azides were obtained by the substitution of bromine or a mesylate group introduced into the jojoba oil molecule; by opening of the epoxide ring in epoxy jojoba; or by the addition of bromoazide to the double bonds of jojoba.     

Optimisation study of large‐scale enzymatic synthesis of oleyl oleate,a liquid wax ester,by response surface methodology

An optimisation study of the large‐scale enzymatic synthesis of a liquid wax ester from oleic acid and oleyl alcohol using Novozym 435 was carried out. Investigations were performed in batch mode with a stirred tank reactor (STR) with one multi‐bladed impeller. Response surface methodology (RSM) based on a five‐level, three‐variable central composite rotatable design (CCRD) was used to evaluate the interactive effects of various parameters. The parameters are amount of enzyme (A) (90–120 g), impeller speed (B) (100–400 rpm) and temperature (C) (40–60 °C). The optimum conditions derived via RSM at a fixed reaction time of 1 h were successfully optimised as A = 104 g, B = 388.0 rpm and C = 49.7 °C. The actual experimental yield was 96.7% under the optimum conditions, which compared well with the maximum predicted value of 97.6%. Copyright © 2005 Society of Chemical Industry     

Hydroxymethylation of jojoba oil by lewis acid-catalyzed ene reaction with formaldehyde

Formaldehyde undergoes ethylaluminum dichloride-catalyzed ene reaction with jojoba oil to afford a mixture of 1∶1 and 1∶2 adducts. The hydroxymethyl products were identified by comparison with model adducts prepared from methyl oleate and oleyl acetate.     

Surface activity of quaternary ammonium salts derived from jojoba oil

A number ofcis andtrans quatenary ammonium salts were synthesized from jojoba oil. All derivatives were found to be surface active agents, i.e., they reduced the surface tension to 35 dynes/cm⁻¹, at very low concentrations. The relationship between the surface activity and the molecular structure is discussed.     

Lipase catalyzed synthesis of oleyl oleate: Optimization by response surface methodology

Lipase catalyzed production of oleyl oleate, which is an analogue of jojoba oil, was carried out using oleic acid and oleyl alcohol in the solvent-free system. Novozym 435, immobilized Candida antarctica lipase, was used as a biocatalyst. Response surface methodology (RSM) based on five-level, four-variable central composite rotatable design was used to evaluate the effects of important parameters on the production of oleyl oleate. Acid/alcohol molar ratio (0.5-1.5), enzyme quantity (2-10% w/w of substrates), reaction temperature (40-60°C), and reaction time (30-90 min) were chosen as process variables for the optimization. Among these parameters, enzyme quantity and acid/alcohol molar ratio have significant effects compared with temperature and time on the production of oleyl oleate. Optimum conditions were found to be a acid/alcohol molar ratio of 1, enzyme quantity of 7% (w/w), reaction temperature of 51°C, and reaction time of 75 min. The coefficient of determination (R 2 ) for the model is 0.97. Probability value is 2.9 ‐ 10 m 9 (P-value<0.01). This P-value demonstrates a very high significance for the regression model. The maximum oleyl oleate concentration predicted by the equation (737 g/L) agrees well with the experimentalvalue (734 g/L) obtained from the experimental verification at the optimum values.     

Lipase-catalyzed synthesis of waxes from milk fat and oleyl alcohol

A screening of five lipases was carried out for the synthesis of wax esters from stoichiometric amounts of oleyl alcohol and milk fat in which long-chain fatty acid content (myristic acid, palmitic acid, stearic acid, and oleic acid) represents 70% of the total fatty acid fraction. The lipases from Alcaligenes sp. and Chromobacterium viscosum both allowed for the best ester synthesis (around 60%) within 2 and 48 h, respectively. Enzeco® Lipase Concentrate gave 30% ester yield within only 2 h. During the time period of 166 h, less than 20% ester synthesis was obtained with Lipozyme? 10,000L whereas Enzeco® Lipase XX did not catalyze the reaction. Owing to commercial availability, the food-grade Enzeco® Lipase Concentrate preparation was selected for further experiments with a view to improve wax synthesis. Wax yields were compared for three substrate molar ratios, i.e., 0.5:1, 1:1, and 1.5:1 (alcohol/fatty acid). For 0.5:1 and 1.5:1 substrate molar ratios, the addition of water increased ester yields while the effect of silica gel addition was shown to be minor. The best improvement was obtained at a substrate molar ratio of 1.5:1 with addition of water, leading to 59% wax ester synthesis.     

Linalyl oleate as a frying oil autoxidation inhibitor

Linalyl oleate (LO), an interesterification product of linalyl acetate (LA) and methyl oleate catalyzed with sodium methoxide, was studied to determine its effectiveness in retarding oxidative changes in soybean oil heated continuously at 180±5°C for 32 h. The identity of LO was established by GC-MS and NMR. LO was tested at levels of 0.05 and 0.1% and compared with the more commonly used synthetic autoxidation inhibitor methyl silicone (MS) at levels of 5 and 10 ppm. FA changes and conjugated dienoic acid formation were monitored. First-order kinetic equations were used to model the decreases in linoleate (18∶2)/palmitate and linolenate (18∶3)/palmitate ratios. Plots of the data show an inflection point at ∼11 h. Oils with either level of MS and LO had lower reaction rate constants before the inflection points, and lower conjugated diene values and higher 18∶2 and 18∶3 percentages at the end of the 32-h heating period than did oil without additives and with LA. LO could replace methyl silicone in soybean oil during deep-fat frying but at levels about 100 times greater. [We propose to use the term “autoxidation inhibitor” for substances that inhibit autoxidation when added to fats and oils at low concentrations and whose mechanism of action may be unknown. Some may wish to call such substances “antioxidants” but others wish to reserve this term for substances that end free radical chains by hydrogen radical donation. Some refer to methyl silicone as a “polymerization inhibitor”, but this term suggests more about its mechanism of action than seems warranted.]     

Retardation effect of jojoba chain length on the chemical reactivity of the liquid wax

Jojoba wax and its derivatives are slow-reacting compounds. To elucidate the reasons for this phenomenon, we reacted jojoba mono- and bis-epoxide and trans-jojoba bis-epoxide (C₃₈–C₄₄ long-chain esters), as well as side chain esters of three steroid skeleton mono-epoxide derivatives with NaI under acidic conditions to yield the corresponding iodohydrins, which then formed the respective bis-keto (or mono-ketone) derivatives. The kinetics, activation energies, and thermodynamic parameters of activation of nucleophilic epoxide opening and pinacol rearrangement were determined for all these compounds. The reaction rates of the jojoba derivatives were similar to those of two of the epoxides derived from the steroid skeleton compounds, and in the third case the steroid derivative reacted somewhat faster than all the rest. This pattern of rate retardation could stem either from folding of the long jojoba chain, resulting in steric hindrance around the reaction centers, or from repeated unproductive collisions along the long hydrocarbon chain of the jojoba wax (statistical effect). Our results appear to suggest that the multiple unsuccessful collisions were the dominant factor, although steric hindrance cannot be ruled out.