Oil from deep water fish species as a substitute for sperm whale and jojoba oils

The lipid fraction of the deep water fish species orange roughy (Hoplostetbus atlanticus), black oreo (Allocyttus sp.) and small spined oreo (Pseudocyttus maculatus) had wax esters with even carbon numbers over the range C₃₀ to C₄₆ as the major components. The component acids and alcohols of the wax ester fraction were analyzed by gas liquid chromatography and compared with those of jojoba and sperm whale oils. Orange roughy oil was refined and deodorized and its chemical, physical and mechanical properties were determined. Hydrogenation of orange roughy oil produced a range of white crystalline waxes with melting points between 34 and 66 C. The characteristics of these waxes were very similar to those of hydrogenated jojoba oil and spermaceti. Lubricant tests performed on sulfurized orange roughy oil indicated it is comparable to sulfurized jojoba and sperm whale oils as an extreme-pressure additive in lubricants. The results show a sound technical basis on which to consider an industry based on orange roughy oil and the oreo oils as replacements for sperm whale oil and as substitutes for jojoba oil. Applications for the oil could be in the cosmetic and high-grade lubricant fields, the waxes in the polish, textile, cosmetic and pharmaceutical industries and the sulfurized derivative of orange roughy oil in the lubricant industry.     

Synthesis of oleyl oleate as a jojoba oil analog

Synthesis of a wax ester analog of jojoba oil was accomplished from oleic acid and oleyl alcohol with a zeolite as catalyst. A full 2³ factorial design at two levels has been used in the synthesis. The variables selected were temperature, reduced pressure and initial catalyst concentration. The most important variable within the range studied was temperature. Reduced pressure had a negative influence, and initial catalyst concentration showed a positive influence on the process. A response equation has been determined for the yield of ester. The properties of the synthesized product are similar to those of natural jojoba oil.     

Jojoba oil analysis by high pressure liquid chromatography and gas chromatography/mass spectrometry

Two analytical procedures for determining com-positions of jojoba liquid wax esters are described and compared. One, the more tedious, involves separation of wax ester homologs by high pressure liquid chro-matography followed by determination of the acid and alcohol moieties from each homolog. The second allows rapid determination of wax ester composition by gas Chromatographic separation of hydrogenated jojoba wax esters according to chain length, followed immediately by ancillary mass spectrometric identifi-cation of the acid and alcohol moieties. Double bonds in the alkyl chains in jojoba liquid waxes were almost exclusively (98%) ω-9, when examined by gas chro-matography/mass spectrometry (GC/MS) and ozonolysis/GC/MS. Presented in part at the 2nd International Conference on Jojoba and Its Uses, Ensenada, Mexico, February, 1976.     

Formation and investigation of microemulsions based on jojoba oil and nonionic surfactants

The properties of jojoba oil make it uniquely suited as a raw material for the cosmetics industry. Water-based, thermodynamically stable preparations of jojoba oil are essential in many formulations. New microemulsions were prepared based on jojoba oil and different nonionic surfactants, namely polyoxyethylene-(ethylene oxide)₁₀-oleyl alcohol (Brij 96V) and ethoxylated sorbitan esters (Tweens). The effects of the surfactants and of primary alcohols as cosurfactants on the isotropic regions of the phase diagram were elucidated. It was found that, up to a certain cosurfactant chain length, the isotropic region expanded considerably as chain length increased. The size of the isotropic region also increased as a function of the ethylene glycol content of the aqueous phase in microemulsions based on ethoxylated alcohol but shrank when ethylene glycol was included in microemulsions prepared with ethoxylated sorbitan esters. Secondary structural phase transitions from water-in-oil to bicontinous and to oil-in-water structures (as determined by measuring conductivity and viscosity) were found to be related to jojoba oil content. Dynamic light scattering and small angle X-ray scattering studies established that incorporation of jojoba oil into Brij 96V micelles caused micellar transformation from elongated to spherical droplets and a decrease in the aggregation number.     

Sulfurized vegetable oil products as lubricant additives

Sulfurized products based on hog fat and its derivatives have extensive commercial use as additives for metalworking and industrial oils, but only relatively small quantities of vegetable oils find such application in North America. Products were made by sulfurization of soybean, sunflower, cottonseed, high erucic rapeseed, canola,Limnanthes (meadowfoam) and prime lard oils. Unlike products from the wax ester jojoba oil, the sulfurized vegetable triglycerides alone had physical properties generally undesirable for lubricant additives. When the oils were sulfurized in the presence of methyl lardate, however, the products had potential practical application. High-sulfur (active) products were made using a 50:50 ratio of triglyceride to methyl lardate, and low-sulfur (inactive) products were made using a 70:30 ratio. Compared to the other sulfurized vegetable triglyceride products,Limnanthes products showed the best solubility in high viscosity-index paraffinic oil. For solutions, measurements of extreme pressure, friction and wear were compared. Whereas products from jojoba were best, of the triglyceride group theLimnanthes-containing products generally gave the best performance. Although this oil had much promise, it is only in its early stage of commercial development. The other vegetable oils also have potential depending on cost and applications. However, overall competition with the well-established, usually lower-cost products from hog fat or greases would appear to be difficult.     

Fatty acids,fatty alcohols,and wax esters fromLimnanthes douglassi (Meadowfoam) seed oil

Limanathes douglasii seed oil glycerides contain fatty acids which predominantly (97%) have 20 or more carbon atoms. Fatty acids were prepared by saponification; fatty alcohols, by sodium reduction of the glycerides; and liquid wax esters, byp-toluenesulfonic acid-catalyzed reaction of the fatty acids with the fatty alcohols. Solid waxes were prepared by hydrogenation of the glyceride oil and of the wax esters. Chemical and physical constants were determined forLimnanthes douglasii seed oil and its derivatives. The liquid wax esters had properties very similar to those of jojoba (Simmondsia chinensis) seed oil. The solid hydrogenated wax ester was identical in physical appearance and melting point to hydrogenated jojoba seed oil. A laboratory of the Northern Utilization Research and Development Division, Agricultural Research Service, USDA.     

Heavily brominated and highly unsaturated derivatives of jojoba oil

Two hexabromojojoba isomers were prepared by bromine addition to bromo-olefinic and bromoallylic derivatives, and an octabromojojoba derivative was prepared from jojobatetraene. Bis-allylic bromination of jojoba wax or monoallylic bromination of jojobatetraene, both followed by HBr elimination, yielded jojobahexaene, which has two conjugated triene units on both parts of the ester. Bromine addition to jojobahexaene yielded dodecabromojojoba, which was unstable toward hydrolysis in water-decalin mixture at 120C., This is in contrast to the relative stability of the octabromojojoba under these conditions. This paper is the fifth in a series of functionalization at the double bond region of jojoba oil.     

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.     

Structural determination and uses of jojoba oil

The predominating molecular species in jojoba oil iscis-13-docosenylcis-11-eicosenoate (erucyl jojobenoate), ranging from 31% to 45% of the extracted seed oil. Other alcohol/acid combinations contribute to the C₄₂ molecular chain length so that this fraction constitutes a low of 41% to a high of 57% of the total wax esters. The positions of the exclusivelycis ethylenic bonds in the alcohol and acid moieties of the wax esters are 99% ω-9 and 1% ω-7. Only 2% of the alcohol and acid moieties were saturated when analyzed after saponification of the oil. Triglycerides were detected by gas chromatography in all of the more than 200 natural jojoba oil samples tested, a few of which had substantially more than the normal 1%. Among the many uses of jojoba oil cited here, the two most promising are the sulfurized oil as extreme-pressure/extreme-temperature lubricant additive and the natural or refined oil formulated into cosmetic products.     

Jojoba oil wax esters and derived fatty acids and alcohols: Gas chromatographic analyses

HCl-catalyzed ethanolysis followed by saponification readily surmounts the resistance of long chain wax esters to direct hydrolysis by alkali. Additionally, choosing ethyl instead of methyl esters allows baseline separations between long-chain alcohols and corresponding esters in gas liquid chromatographic (GLC) analysis of total alcohol and acid components before saponification. Liquid wax esters were analyzed on a temperature-programmed 3% OV-1 silicone column. Geographical and genetic effects on the variability of jojoba oil composition were investigated with five different seed samples. Major constituents in jojoba seed oil from shrubs in the Arizona deserts, as indicated by GLC analyses of oil, ethanolysis product, isolated fatty alcohols and methyl esters of isolated fatty acids, were C₄₀ wax ester 30%, C₄₂ wax ester 50% and C₄₄ wax ester 10%; octadecenoic acid 6%; eicosenoic acid 35%, docosenoic acid 7%, eicosenol 22%, docosenol 21% and tetracosenol 4%. Oil from smaller leaved prostrate plants growing along California’s oceanside showed a slight tendency toward higher molecular size than oils from the California desert and Arizona specimens. The wax esters are made up of a dispro-portionately large amount of docosenyl eicosenoate and are not a random combination of constituent acids and alcohols.Lunaria annua synthetic wax ester oil was used as a model for evaluating the analytical procedures. Presented at the AOCS Meeting, Chicago, September 1970 No. Utiliz, Res. Dev. Div., ARS, USDA.     

Oxidative stability of jojoba wax

The rates of autoxidation of crude, bleached and stripped jojoba wax were determined under conditions of accelerated oxidation (98 C). Oxidation of the raw yellow wax had a long induction period (50 hr) compared with the bleached wax (10–12 hr) or stripped wax (2 hr). These differences indicate the presence of a natural antioxidant in the crude wax. Addition of 0.02% butylated hydroxytoluene or butylated hydroxyanisole to the bleached wax restored and even improved its stability. Autoxidation of jojoba wax was also studied at room temperature. In the presence of light and air, the activity of the natural inhibitor was rapidly lost.     

Long-chain unsaturated alcohols from jojoba oil by sodium reduction

Summary Jojoba oil is a liquid wax composed essentially of C₂₀ and C₂₂ straight-chain monoethylenic acids and alcohols in the form of esters. Sodium reduction of the wax fatty esters in jojoba oil yielded quantitatively a mixture of unsaturated, long-chain alcohols from the acid moiety of the jojoba oil. Yields of about 91% were obtained in the laboratory-scale experiments and 82 to 86 for the pilot-plant experiments. Analytical data, including detailed infrared spectra information, are given for the resulting product alcohols. Presented at the fall meeting, American Oil Chemists' Society, Cincinnati, O., September 29-October 2, 1957. One of the laboratories of the Southern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

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: I. bromine derivatives

Addition of bromine to jojoba oil and itstrans-isomer yielded tetrabromojojoba, which upon elimination afforded the acetylenic and allenic components, respectively, when reacted with excess of base. The bromoolefinic products were obtained when limited amount of base was used. Allylic bromination of the liquid wax and itstrans-isomer, and subsequent HBr elimination, yielded the two conjugated diene systems on both parts of the ester (jojoba tetraene).     

Differential scanning calorimetry index for estimating level of saturation in transesterified wax esters

Differential scanning calorimetry (DSC) thermograms of fatty esters can give valuable information on melting characteristics and heats-of-fusion enthalpy (ΔH). A series of jojoba liquid wax esters was constructed by transesterifying native jojoba oil with 5–50% completely hydrogenated jojoba wax esters. This series, when subjected to a standardized DSC tempering method with heating/cooling cycles, exhibited an excellent correlation for level of saturation based on area changes in endothermic ΔH. Endothermic events were recorded for native (ΔH_A) and completely hydrogenated (ΔH_C) jojoba wax esters. A third endotherm, ΔH_B, was observed when they were transesterified. Based on a multiple regression program, the best fit (R²=0.98) using ΔH data was: % saturation=16.847–0.162 (ΔH_A)+0.209 (ΔH_B)+0.600 (ΔH_C). Standard errors for predictions were approximately 1.045 at 0% saturation, 0.770 at 25% saturation, and 1.158 at 50% saturation. Endothermic events A, B, and C each represent the respective diunsaturated, mounounsaturated, and saturated contents of wax esters in the transesterified blends. This was verified by measuring the dropping points for both the native and completely hydrogenated wax esters. These findings provide an index which can predict the degree of saturation in transesterified wax ester blends and serves as a research tool in process and product developments. Presented at the 1995 AOCS Meeting, May 7–11, 1995, San Antonio, Texas. Retired.     

Rapid ethanolysis procedure for jojoba wax analysis by gas liquid chromatography

A rapid ethanolysis procedure for preparing jojoba wax for gas liquid chromatographic analysis is described. The wax esters are hydrolyzed by refluxing 4 drops of jojoba wax in 5% HCl in anhydrous ethanol in a test tube. The resulting fatty acid ethyl esters and fatty alcohols are separated and quantitated by a single gas liquid chromatographic run. Analysis of duplicate samples by this procedure gives essentially the same results as a procedure which requires 10 times more sample and reagents and considerably more time.     

Routine analysis of jojoba wax fatty acids and alcohols by single column capillary GC

Through a detailed study of the different steps and reactions of the ethanolysis and acetylation of jojoba wax, two analytical procedures were developed. One method could be a standard method of analysis because it includes a one-pot derivatization of the jojoba wax followed by a single GC analysis with an overall analysis time of three hr. The other method, is suitable for the analysis of large numbers of samples for checking, screening, selection and breeding among the different jojoba genera.     

Wax esters and triglycerides as storage substances in seeds of Buxus sempervirens

The seeds of the evergreen Buxus‐tree, Buxus sempervirens, contain a yellowish oil which represents up to 42% of the dry weight. The oil consists, in comparison to the lipids of jojoba fruits (Simmondsia chinensis), of only 3.6% wax esters. 95% of the oil consist of triglycerides, the typical storage substances of oil fruits. Phospholipids occur with 0.4% and glycolipids with 0.13%. The fatty acid patterns of these lipids correspond to the typical fatty acid compositions of the respective lipid classes. In the wax esters monoenoic fatty acids and saturated fatty acids with 16 and 18 carbon atoms prevail. The glycolipid and phospholipid fractions are characterized by a high portion of dienoic and monoenoic as well as saturated fatty acids having 16 and 18 carbon acids.     

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.     

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.