Evaluating the Oil‐Gelling Properties of Natural Waxes in Rice Bran Oil: Rheological,Thermal, and Microstructural Study

The main objective of this research was to enhance the understanding of the oil‐structuring properties of natural waxes. A number of natural food‐grade waxes were evaluated for their oil‐gelling properties using a combination of techniques, including rheology, differential scanning calorimetry, and polarized light microscopy. Based on the rheological measurements (oscillatory, flow, and thixotropic behavior), we found that rice bran wax, carnauba Brazilian wax and fruit wax showed weak gelling behavior in rice bran oil (prepared at concentrations as high as 5 % w/w), exhibiting relative low elastic moduli that displayed a high frequency dependency. On the contrary, carnauba wild wax, berry wax, candelilla wax, beeswax, and sunflower wax were efficient oleogelators forming strong gels at concentration of <2 % w/w. We attempt to explain these observed differences in gelling behavior by crystal morphology, network formation, and the final amount of crystalline phase.     

Chemical Modification of Partially Hydrogenated Vegetable Oil to Improve its Functional Properties for Candles

Partially hydrogenated vegetable oil (PHVO) has recently been used to make vegetable oil-based candles. However, its use is limited primarily to container candles because of its inherent physical properties, such as brittleness when a hard material is produced, and greasiness when it is soft by low degree of hydrogenation. Such material lacks the most desired cohesiveness and elasticity compared to the commercial petroleum paraffin and beeswax. To improve the cohesiveness and thermal properties of PHVO, epoxidation, ring-opening reaction, and esterification were conducted to introduce new functional groups into the fatty acyl chain of PHVO. These newly synthesized derivatives or waxes were also mixed with the fully hydrogenated soybean oil (FHSO) or PHVO base materials. Hardness and cohesiveness of the new waxes and the mixtures were measured with a texture analyzer. Their thermal properties were analyzed with a differential scanning calorimetry (DSC). It was found that the introduction of hydroxyl (OH) group significantly improved the cohesiveness of PHVO. The melting range of PHVO also increased after the reactions. However, the hardness of the new wax was lower than those of commercial paraffin wax or beeswax. For wax mixtures, the hardness of dihydroxy wax was significantly improved by the addition of FHSO, however, the cohesiveness was negatively affected by the amount of FHSO added. Both the melting and the crystallization ranges were widened by mixing the derivatives with the base materials.     

Physical Properties of Beeswax,Sunflower Wax,and Candelilla Wax Mixtures and Oleogels

To be able to tailor and optimize the physical properties of oleogels for various food applications, more information is needed to understand how different gelators interact. Therefore, the objectives of this study were to evaluate the interactions between binary mixtures of beeswax (BW), candelilla wax (CLW), and sunflower wax (SFW) in pure form as well as in 5% wax oleogels made with soybean oil, in terms of their crystallization and melting properties, crystal morphology, solid fat content, and gel firmness. CLW:BW mixtures had eutectic melting properties, and oleogels from these mixtures with 40:60 to 90:10 CLW:BW were firmer compared to oleogels made with one wax. The main components in SFW and BW appeared to cocrystallize or crystallize at the same temperature, but nonlinear changes in melting point and solid fat content profile of oleogels prepared with the mixed waxes indicated that SFW dominated oleogel formation. In addition, oleogels prepared with mixtures of SFW and BW had lower firmness compared to oleogels prepared with one wax, indicating an incompatibility between the two waxes. The main wax components in SFW and CLW never cocrystallized, and low levels of CLW appeared to prevent SFW from forming a crystalline platelet network. This resulted in low firmness of oleogels made from mixtures of 90:10 to 60:40 SFW:CLW compared to oleogels prepared with one wax. However, the firmest oleogels of all mixtures were made from 10:90 SFW:CLW. Changes in gel firmness and melting properties with mixed wax oleogels were likely to be due to changes observed in the crystal size and morphology. In addition, the firmest gels were shown to result from mixtures that were predicted to have >40% hydrocarbon content, and a high hydrocarbon to wax ester ratio, but minor components such as free fatty acids and fatty alcohols may have also influenced firmness.     

Determining the structure and stability of essential oil-sunflower wax and beeswax oleogels

In this study, essential oil oleogels were produced using eucalyptus, lavender, lemon peel and tea tree oils with sunflower and beeswax. The physicochemical, thermal, textural, and structural features of the oleogels were determined. For the essential oils used, an addition level of less than 15% of beeswax (BW) was insufficient to form stable oleogels, whereas an addition level of 10% of sunflower wax (SW) was sufficient to form stable oleogels. The acid and peroxide values of the gels were higher than those of the oils. All of the oleogels exhibited peaks around 3.70 and 4.10, indicating the presence of β' polymorphic forms. The hardness and stickiness values of the oleogels were influenced by the type and level of wax addition, as well as the viscosity of the oil used. Based on the thermal analysis results, the oleogels based on beeswax exhibited lower melting properties compared to those based on sunflower wax. The thermogravimetric data indicated that the polymeric matrices formed by the waxes, which depended on the type and level of wax addition, affected the vaporization of the volatiles. In conclusion, oleogels represent a green and sustainable approach for reducing the loss of volatile or bioactive compounds from various essential oils, which are widely used in the food, cosmetics, and pharmaceutical industries.     

A comparison of six solvents for the extraction of jojoba seed

Summary Data are presented which show the effects of different solvents on the yield and properties of liquid wax fromSimondsia chinensis (jojoba) and on the characteristics of the hydrogenated waxes obtained from the liquid waxes. Three reagent grade solvents, carbon tetrachloride, benzene, and isopropyl alcohol, and three commercial grade solvents, heptane, hexane, and tetrachloroethylene, were evaluated as extractants for the liquid wax from jojoba. Soxhlet-type of extractions were carried out under conditions in which the solvent was the only significant variable. Four of the solvents extracted essentially the same amount of material from the seed while isopropyl alcohol extracted significantly more material and tetrachloroethylene significantly less. Obviously the difficulties involved in separating the solids recovered from the isopropyl alcohol extraction preclude its use as the extracting solvent for jojoba wax. The density of the liquid waxes varies from 0.8631 to 0.8648; the waxes from the tetrachloroethylene and hexane extractions had the lowest value and the wax from isopropyl alcohol the highest. In each case, regardless of the solvent used, a precipitate developed in the liquid wax after it had been desolventized and stored for 7–10 days. Hydrogenation of clear fractions and precipitate containing fractions of these liquid waxes showed that the precipitate had no apparent effect upon the melting point or hardness of the resulting solid wax. Some of the liquid waxes required a longer hydrogenation time to attain an iodine value of about 1. At this iodine value all of the solid waxes had melting points between 66 and 68°C. Hardness values of all the solid waxes as measured by the Trionic hardness gauge were 90. One of the laboratories of the Southern Utilization Research and Development Division, Agricultural Research Service, U. S. Department of Agriculture.     

Wax composition of sunflower seed oils

Waxes are natural components of sunflower oils, consisting mainly of esters of FA with fatty alcohols, that are partially removed in the winterization process during oil refining. The wax composition of sunflower seed as well as the influence of processing on the oil wax concentration was studied using capillary GLC. Sunflower oils obtained by solvent extraction from whole seed, dehulled seed, and seed hulls were analyzed and compared with commercial crude and refined oils. The main components of crude sunflower oil waxes were esters having carbon atom numbers between 36 and 48, with a high concentration in the C₄₀−C₄₂ fraction. Extracted oils showed higher concentrations of waxes than those obtained by pressing, especially in the higher M.W. fraction, but the wax content was not affected significantly by water degumming. The hull contribution to the sunflower oil wax content was higher than 40 wt%, resulting in 75 wt % in the crystallized fraction. The oil wax content could be reduced appreciably by hexane washing or partial dehulling of the seed. Waxes in dewaxed and refined sunflower oils were mainly constituted by esters containing fewer than 42 carbon atoms, indicating that these were mostly soluble and remained in the oil after processing.     

Structure and Physical Properties of Plant Wax Crystal Networks and Their Relationship to Oil Binding Capacity

The microstructure, melting and crystallization behavior, rheological properties and oil binding capacity of crystalline networks of plant-derived waxes in edible oil were studied and then compared amongst different wax types. The critical concentrations for oleogelation of canola oil by rice bran wax (RBX), sunflower wax, candelilla wax, and carnauba wax were 1, 1, 2, and 4 %, respectively, suggesting RBX and sunflower wax are more efficient structurants. A phenomenological two-phase exponential decay model was implemented to quantify the oil-binding capacity of these oleogels. Parameters obtained from this empirical model were then evaluated against microscale structural attributes such as crystal size, mass distribution and porosity to determine the structural dependence of oil-binding capacity. Gels containing candelilla wax exhibited the greatest oil-binding capacity, as they retained nearly 90 % of their oil. This is due to the small crystal size as well as the spatial distribution of these crystals. Using a microscopic to macroscopic approach, this study examines how the structural characteristics unique to each wax and resulting oleogel system affect functionality and macroscopic behavior.     

Effects of physical refining on contents of waxes and fatty alcohols of refined olive oil

Changes in the contents of waxes and fatty alcohols during deodorization/physical refining of bleached olive oil were studied. Experiments were carried out with 1.85% acidity oil, which was physically refined in a discontinuous deodorizer of 250-kg maximum capacity using nitrogen as stripping gas instead of steam. The variables studied were load and temperature of oil in the deodorizer as well as N₂ flow. Analyses of waxes and alcohols were carried out at different operation times. The maximum content of wax was always observed when the oil reached the deodorization temperature. The variation in the wax content depended on temperature and N₂ flow. Wax decomposition started and continued during the operating time, and a progressive decrease, which was pronounced between 3 and 4 h, was observed. Small changes in waxes were observed between 4 and 5 h. Total content of fatty alcohols diminished throughout the operating time, and changes did not depend on the variables studied.     

Effect of Storage Time on Wax–Wax–Hydrolyzate Canola Oil Oleogels

In this study, two natural waxes, beeswax (BW) and sunflower wax (SFW), are combined with their hydrolyzed variants to deliberately alter the waxes’ composition. The properties of the produced oleogels with different wax inclusion levels (4%, 8%, 12%, and 16% w/w) are investigated after defined intervals (2 days, 7 days, 3 weeks, and 3 months). To do so, the gels are monitored via penetrometry, microscopy, and calorimetry. Although the gels do not show any significant difference during storage in the micrographs, the calorimetric and firmness data reveal meaningful results. The heat of dissolution increases in every system investigated, indicating post-crystallization processes. Due to different solubilities of wax components, the critical gelling concentration is determined and the solid wax content is retrieved to further address the structure efficiency (S.E.). It is demonstrated that although the quantity of solids over time increases, the scaffolding effectiveness decreases in most cases. Only SFW, most likely due to sintering, shows an increase in S.E. over the storage time. Identified synergistic effects in BW and hydrolyzate mixtures decrease with increasing storage time. This work aims to contribute to a better understanding of the behavior of wax-based oleogels upon storage. Practical Applications: Although much is known about the gel properties of wax-based oleogels at short-term, the behavior over the storage period remains largely unresolved. However, this behavior is immensely important for a real application in fast and slow moving consumer goods. After all, products should always have the same consumer-relevant properties when stored at variable time frames. This applies to both food and pharmaceutical products. Knowledge of the behavior of wax-based oleogels in terms of a time-dependent change can help to choose a targeted product design and ensure product quality and consumer satisfaction.     

A Simplified Method for Fractionation and Analysis of Waxes and Oils from Sorghum (Sorghum bicolor (L.) Moench) Bran

In the United States, sorghum is primarily used for animal feed and ethanol production but has potential to provide value-added coproducts including waxes and oil. The surface of sorghum contains 0.1–0.4% wax; however, wax extraction from whole kernels before fermentation may not be economical. An alternative method for this extraction could be facilitated through decortication, abrasion of the surface to remove bran. Decortication increases the starch content of decorticated sorghum, potentially improving ethanol yields, while concentrating wax and oil to the bran. Typically, oil (triacylglycerols) and waxes are extracted from bran in one extraction and waxes are precipitated from oil using cold temperatures then filtration. This research compared traditional fractionation (simulated with a two-step, single-temperature extraction) to a two-step, dual-temperature extraction, whereby oil is first extracted at room temperature and then waxes at elevated temperature. Extractions were performed using an accelerated solvent extractor with hexane or ethanol as solvents. Ethanol extraction showed greater yields (~15% w/w) compared to those of hexane (~11% w/w) because polar materials were extracted. Using hexane, the two-step, dual-temperature fractionation separated waxes from oils via the temperature of extraction solvent with similar purity to the traditional method that fractionated via cold precipitation and filtration. For ethanol, the traditional single-step method fractionated with higher wax purity but lower oil purity compared to the two-step, dual-temperature fractionation.     

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.     

Co-crystals of Beeswax and Various Vegetable Waxes with Sterols Studied by X-ray Diffraction and Differential Scanning Calorimetry

In this study, mixtures of purified wax and sterols were melted and subsequently cooled. Using X-ray diffraction of the mixed, solid phase, it was shown that for up to 30–40 wt% sterols no measurable re-crystallisation of sterols occurred, i.e. the sterols became dissolved at a molecular level. Probably a form of amorphous co-crystals of sterols and wax is formed if the molecular ratio does not exceed 1:1. Differential scanning calorimetry (DSC) suggests that a minor amount of pure sterols could already be present at lower sterol levels. This may be because of the higher temperature at which the microstructure is probed when using DSC—melting of the wax might lead to crystallisation of the sterols. For application in foods, the structure as probed by X-rays at ambient temperatures is more relevant. When sunflower wax and rice bran wax are used, prevention of sterol crystallisation is even more pronounced, probably because the melting temperatures of these waxes are closer to the melting temperature of sterol crystals. Replacing the beeswax with a saturated fat (heRP70), sunflower oil, or jojoba wax (a liquid wax) substantially increases the amount of crystalline sterols. The difference between the various waxes and fats was qualitatively the same for X-ray diffraction and DSC. Stanols can be incorporated in the same manner and up to similar concentrations. Another insoluble nutritional compound, ursolic acid, has a greater tendency to crystallise in wax. This is probably because the melting temperature of ursolic acid is much higher than that of wax.     

Wax analysis of vegetable oils using liquid chromatography on a double-adsorbent layer of silica gel and silver nitrate-impregnated silica gel

A chromatographic method is described to measure the crystallizable wax content of crude and refined sunflower oil. It can also be applied to any other vegetable oil. The preparative liquid chromatography step on a glass column containing a silica gel adsorbent superimposed upon a silver nitrate-impregnated silica gel support is used to isolate a wax fraction which is then analyzed by gas chromatography. The recovered wax fraction contains, in addition to the crystallizable waxes, hydrocarbons and other compounds with gas chromatographic retention times corresponding to waxes with chain lengths C₃₄−C₄₂. These compounds are short-chain saturated waxes in fruit oils, such as grapeseed and pomace. In seed oils such as sunflower, soybean or peanut, the compounds initially referred to as “soluble esters” are identified as monounsaturated waxes, esters of long-chain saturated fatty acids, and a monounsaturated alcohol, mainly eicosenoic alcohol. Such waxes are absent from corn or rice bran oils.     

Acyl-acyl carrier protein pool dynamics with oil accumulation in nitrogen-deprived Chlamydomonas reinhardtii microalgal cells

Microalgae are potential biofuel feedstocks for production of energy-dense triacylglycerols (TAG). Nitrogen deprivation is known to trigger microalgal TAG accumulation by upregulation of de novo fatty acid (FA) biosynthesis through chloroplast-localized Type II FA synthases (FAS). To gain insights into the associated FAS regulatory mechanisms, we applied a recently reported liquid chromatography–mass spectrometry method to examine acyl-acyl carrier protein (ACP) pool compositional changes of the microalga Chlamydomonas reinhardtii over a nitrogen deprivation time-course. We observed that acyl-ACP pools are highly enriched in acetyl-ACP in nutrient-rich media in photoheterotrophically grown cells. Following shift to nitrogen deprivation, acetyl-ACP markedly decreased, and long-chain palmitoyl (16:0)-, stearoyl (18:0)-, and oleoyl (18:1)-ACPs progressively predominated in acyl-ACP pools in parallel with increases in FA and TAG production. This study shows the utility of microalgal cells to study acyl-ACP pool dynamics to gain insights into plant FA biosynthetic regulation and oil enhancement strategies.     

Synthesis of comb‐type copolymers with various pendants and their effect on the complex rheological behaviors of waxy oils

To improve the flowability of waxy crude oil containing a high concentration of asphaltenes (AS), novel comb‐type copolymers of poly(maleic acid polyethylene glycol ester‐co‐α‐octadecene) (PMAC) and poly(maleic acid aniline amide‐co‐α‐octadecene) (AMAC) with various grafting ratios (R_g) of PEG/aniline to maleic anhydride are synthesized. Model oils containing wax mixtures and AS are prepared to explore the effect of asphaltene concentration and the copolymers on the yield stress. The influence of the copolymers on the wax appearance temperature (WAT) of Liaohe high waxy oil is examined by rheological and microscopic methods. Experimental flow curves of shear stress as a function of shear rate are fitted following the Casson model to interpret the rheological properties of gelled waxy crude oil in the presence of AMACs, PMACs, and MAC. Compared with MAC, PMACs, and AMACs are more efficient in reducing the yield stress of both model oil and crude oil, which indicates a better flowability. It is found that PMAC1.0 and AMAC1.0 with a medium R_g can balance the interaction of copolymers with waxes and AS and reduce the yield stress much more than others. Between them, AMAC1.0 that possesses aromatic pendants is better than PMAC1.0, which only has polar pendants. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41660.     

Evaluation of Beeswax,Candelilla Wax,Rice Bran Wax,and Sunflower Wax as Alternative Stabilizers for Peanut Butter

Four natural waxes were evaluated as stabilizers in peanut butter. The potential advantage of using natural waxes would be the replacement of current stabilizers such as hydrogenated or tropical oils, thereby reducing saturated fats and satisfying clean label requirements. Beeswax (BW), candelilla wax (CLW), rice bran wax (RBW), sunflower wax (SFW), and a commercial peanut butter stabilizer, hydrogenated cottonseed oil (HCO), were added to three natural peanut butter brands at levels ranging from 0.5% to 2.0% (w/w) and tested for accelerated oil release, long-term stability, firmness, and rheology. At levels ≥0.5%, all waxes improved oil-binding capacity (OBC). SFW and HCO had the highest OBC, followed by RBW, CLW, and BW. All waxes reduced the amount of oil separation after 6 months at 22 ± 2 °C. HCO followed by SFW reduced oil separation the most, but there were no significant differences between stabilizers at 1–2%. Firmness and yield stress increased with increasing stabilizer level, with SFW increasing firmness the most, followed by HCO, RBW, and CLW, while BW had the lowest effect. The results indicate that the waxes may be feasible replacements for hydrogenated oils as peanut butter stabilizers, but levels would need to be optimized depending on the product characteristics and wax type.     

Chemometric Classification of Comb and Cuticular Waxes of the Honeybee Apis Mellifera Carnica

Waxes are important as building material and for the chemical communication of the honeybee Apis mellifera carnica. In this study chemometric tools were established for classifying the different waxes inside the hive. By using gas chromatography in combination with mass spectrometry, components of different types of waxes were analyzed. By considering different substance classes of waxes, discriminant function analyses revealed distinct subtypes of comb waxes and of cuticular waxes. It is shown that the aging of comb wax is in part a spontaneous physicochemical process due to differential volatilities of compound classes with different chain length ranges. On the other hand it is directly influenced by the bees by adding lipolytic enzymes to the comb wax. The data suggest that the varying cuticular wax and comb wax compositions could serve as cues for bees to recognize castes, sexes, or comb age.     

The compositions of some unhydrolyzed naturally occurring waxes,calculated using functional group analysis and fractionation by molecular distillation,with a note on the saponification of carnauba wax and the composition of the resulting fractions

Summary Methods for the determination of acid, ester, hydroxyl, and ketone (or aldehyde) groups and of mean molecular weights of small samples of natural waxes are reported. Complete analyses can be made on 0.5 g. of sample. A simplified procedure for quantitative separation of acid and unsaponifiable fractions of a wax is also reported. Molecular distillations of beeswax, caranda wax, crude and refined candelilla wax, and ouricury wax, have fractionated these complex mixtures into simpler ones. Hydrocarbons and free unsubstituted alcohols and acids, if present, distil readily at 150°C. A pot still suitable for convenient molecular distillation of up to 100-g. charges of waxes or other high melting materials is described. A method for the calculation of composition of unhydrolyzed waxes based upon function group analysis of molecular distillation fractions is described. Results of application of this method to the waxes distilled are reported and show the ubiquitousness of hydroxy acids. All of the above waxes and carnauba wax contain major proportions of esters of the hydroxy acids, and none contains as much as one-half simple esters of unsubstituted acids and alcohols. A portion of a dissertation submitted by Thomas Wagner Findley to the Graduate School of the Ohio State University in partial fulfilment of the requirements for the Ph.D. degree. S. C. Johnson and Son Inc. Fellow in Physiological Chemistry, 1946-50.     

Characterization of laurel fruit oil from Madeira Island,Portugal

The fixed oil extracted from Laurus spp. fruit from Madeira Island, Portugal, is used in local traditional medicine for a wide variety of health complaints. Physical properties, density and refractive index, as well as the TAG FA composition, sterols, and waxes were determined. The oil was found to have an unusually high content of volatiles (ca. 10%), with trans-ocimene and germacrene D predominating. Oleic (30%) and linoleic (20%) acids were the main unsaturated FA, whereas lauric (18%) and palmitic (up to 22.5%) acids were the main saturated FA in the neutral lipid fraction. The oil had a sterol content on the same order as olive oil, with β-sitosterol (84%) predominating. Two sesquiterpene lactones, dehydrocostuslactone and costunolide, accounted for 5% of the overall composition. Madeira laurel oil is not currently used as an edible oil because of its very strong flavor. Its claimed medicinal properties have not yet been validated, and this is the first report on the characterization of the commercial product.