Mechanical properties of wax-oleogels: Assessing their potential to mimic commercial margarine functionality under small and large deformations.

Utilizing waxes to gel oils presents a viable approach for diminishing trans and saturated fat levels in commercial fats such as margarines. This technique ensures that oleogels mimic traditional fats in terms of rheological properties, oil-binding capacity, and overall structure. Our study employed cooling-shear rates to finely adjust physical characteristics, evaluating rheology via SAOS-LAOS, oil retention, and crystal structure of wax oleogels, compared against commercial margarines as benchmarks. Findings indicate that wax oleogels, under specific cooling/shear conditions, exhibit softer yet more ductile-like behavior, akin to margarine, while retaining oil effectively. This similarity is evidenced through Lissajous curves and plastic dissipation ratio during yielding, reflecting a ductile yielding response characterized by square-like Lissajous curves and a plastic dissipation ratio index approximating one. Although these crystallization conditions influence the mechanical properties of wax oleogels, they do not alter oil losses or wax characteristics.

The relationship between nonlinear viscoelasticity and baking performance in low-saturated puff pastry margarine.

The oil phase obtained by blending and oleogel methods has potential for the production of non­hydrogenated and low-saturated puff pastry margarine, thereby reducing intakes of both types of dietary fat. The crystal form, microstructure, rheology, and baking applications of puff pastry margarines prepared with anhydrous milk fat (AMF)/palm stearin (POs), POs/palm oil (PO), beef tallow (BT)/PO, or AMF/POs/diacetyl tartaric acid ester of mono(di)glycerides (DATEM) oleogels were investigated using X-ray scattering, polarized light microscope, and rheometer, respectively. All margarines exhibited ß'-form crystal and strongly viscoelastic at low strain. With the addition of DATEM oleogel, their crystal microstructure became more uniform and finer, and the croissants were less hard (1690) and chewiness (160). The chewiness of croissants produced using the margarines was significantly improved with POs content. The theoretical basis for preparation and application in non­hydrogenated and low-saturated puff pastry margarine was provided in the present study.

Alginate/whey protein isolate-based emulgel as an alternative margarine replacer in processed cheese: Impact on rheological, mechanical, nutritional, and sensory characteristics.

The effects of partial or full replacement of margarine by alginate/whey protein isolate-based olive oil emulgel on nutritional, physicochemical, mechanical, and rheological properties of processed cheese (PC) were investigated in this work. All formulated samples had the same amount of total fat, DM, and pH. According to the results of the fatty acids profile, the PC sample in which the margarine was fully replaced by the emulgel (EPC100) had the highest (49.84%) oleic acid content and showed a reduction of 23.7% in SFA compared with the control sample (EPC0; formulated just with margarine). In addition, EPC0 had the highest hardness among various cheese samples, which was also confirmed by its compact microstructure. Dynamic oscillatory measurements revealed that EPC100 had the highest crossover strain (or resistance to deformation). The high rigidity of this sample was related to the 3-dimensional structure of emulgel. According to the creep test results, EPC100 showed the lowest relative recovery (flowability). A high temperature dependency of viscoelastic moduli was observed in EPC0 at 42°C. No significant differences were observed between the color attributes and sensory properties of the various cheese samples. Alginate/whey protein isolate-based olive oil emulgel can be considered as a healthy margarine replacer in PC.

Structural behavior, FTIR spectra of five Algerian honeys, and sensory acceptance of margarine enriched with honey.

This study examined the textural and rheological properties of Algerian honeys and margarines formulated with honey and their sensory acceptance. Textural analysis shows that all honeys and margarines enriched with honey are spreadable, easy to swallow by the consumer and to adhere to a surface (bread, teeth, tongue, etc.), and have suitable adhesiveness. The hardness and elasticity values reveal that H5 honey and its M5 margarine are less hard and regain their height more quickly. The rheological analysis reveals that all honeys and formulated margarines non-Newtonian behavior at 25 and 45°C with a G' > G″ for each type of honey except for H1 and all margarines elaborated with honey presenting a structure of a gel. Statistical analysis shows no significant differences (p > 0.05) in mean values of activation energy, suggesting that honeys and margarines need the same energy to flow. Chemometric analysis reveals strong similarities between (H3 and H5) and (M3 and M5). Sensory acceptance of margarines enriched with honey shows that M4 and M5 margarines are the most preferred by consumers with a satisfaction rate between 60% and 80%. In conclusion, margarine formulated with honey should be introduced to the market due to their good structural properties and high acceptance.

The effect of preparation temperature and composition on bigel performance as fat replacers.

Consumer awareness of the deleterious effect of a diet rich in saturated fat pushes the food industry to find new fat alternatives. Bigels, hybrids of hydrogels and oleogels, are an attractive option for formulating oil-based fat mimetics, particularly lamination fats. This research explored the characteristics of a hydrogel-in-oleogel bigel, made of candelilla wax and xanthan gum. This study investigated the effect of homogenization temperature, hydrogel : oleogel phase ratio, and storage conditions on the bigel melting profile, mechanical and rheological properties, stability, and the structural characteristics involved. The optimal homogenization temperature that resulted in a smooth, firm, margarine-like texture was 42 °C while higher homogenization temperatures produced lumpy unspreadable bigels and lower ones produced soft and smooth texture. The bigel behavior was related to the formation of a low mobility biphasic system, stabilized in a Pickering mechanism by wax crystals that crystallize at 47 °C, above the homogenization temperature. The phase ratios tested, 15 : 85 to 45 : 55 hydrogel : oleogel, appeared to have a limited effect on any of the bigel characteristics. More specifically, no significant differences in melting temperature, texture parameters, flow behavior, and stability, which are reminiscent of margarine, were detected. These results indicated that hydrogel droplets may serve as active fillers, strengthening the bigel matrix when their amount in the bigel increases and the oleogel, which is the dominant phase, decreases. These findings provide an understanding of the way bigel properties depend on the formulation and preparation, which is valuable in the development of bigel fat replacers and other novel food applications.

Development of a QuEChERS method for simultaneous analysis of 3-Monochloropropane-1,2-diol monoesters and Glycidyl esters in edible oils and margarine by LC-APCI-MS/MS.

A simple, fast and effective direct method based on HPLC-APCI-QqQ-MS/MS has been developed to simultaneously determine four 3-monochloropropane-1,2-diol monoesters (3-MCPDE) esterified with palmitic, linoleic, stearic, and oleic acid, and two glycidyl esters (GE) with palmitic and oleic acid in margarine and olive oil using a QuEChERS approach. Factors affecting the efficiency of the extraction process were assessed, including type and amount of salt, extraction solvent, test portion amount, and clean-up sorbent. The analytical method was validated according to Food and Drug Administration (FDA) guidelines using matrix-matched calibration with internal standards and showed good results in terms of linearity (r2 > 0.9992), accuracy (80

Crystallization and Structural Properties of Oleogel-Based Margarine.

Interest in oleogel as a promising alternative to traditional hydrogenated vegetable oil has increasingly grown in recent years due to its low content of saturated fatty acids and zero trans fatty acids. This study aimed to develop wax-based margarine to replace traditional commercial margarine. The wax-based margarine was prepared and compared with commercial margarine in texture, rheology, and microscopic morphology. The possibility of preparing margarine at room temperature (non-quenched) was also explored. The results showed that the hardness of oleogel-based margarine increased as the BW concentration increased. Denser droplets and crystal network structure were observed with the increase in BW content. XRD patterns of oleogel-based margarine with different content BW were quite similar and structurally to the ß' form. However, the melting temperature of oleogel-based margarine was over 40 °C at each concentration, which represented a poor mouth-melting characteristic. In addition, the unique, improved physical properties of oleogel-based margarine were obtained with binary mixtures of China lacquer wax (ZLW) and Beeswax (BW), due to the interaction of the ZLW and BW crystal network. The rapid cooling process improved the spreadability of oleogel-based margarine. The margarine prepared by 5% BW50:ZLW50 had similar properties to commercial margarine in texture and melting characteristics (37 °C), which had the potential to replace commercial margarine.

Quantitative Analysis of Lactone Enantiomers in Butter and Margarine through the Combination of Solvent Extraction and Enantioselective Gas Chromatography-Mass Spectrometry.

We quantified the enantiomeric distributions of δ- and γ-lactones in butter, fermented butter, and margarine through the combination of solvent extraction and enantioselective gas chromatography-mass spectrometry. The main lactones in butter and fermented butter comprised (R)-δ-decalactone, (R)-δ-dodecalactone, (R)-δ-tetradecalactone, (R)-δ-hexadecalactone, and (R)-γ-dodecalactone. In contrast, margarine samples consisted of only δ-decalactone and δ-dodecalactone in racemic forms, indicating that synthetic aroma chemicals were added to margarine. After heat treatment, 13 types of lactones were detected in butter and fermented butter. In heated butter and fermented butter, major δ-lactones in the (R)-form were abundant, but only δ-octalactone in the (S)-form was detected. In contrast, γ-dodecalactone (main γ-lactone in the heated samples) was abundant in the (R)-form, whereas other γ-lactones were detected in the racemic form. These results suggested that the major lactones in dairy products are in the (R)-form. Furthermore, the heat treatment affected the enantiomeric distribution of lactones in butter and fermented butter.

Fractionated palm oils: emerging roles in the food industry and possible cardiovascular effects.

The public health debate about fats and human health has been ongoing for a long time. Specifically, the fat types commonly used in the food industry and the techniques used in extracting them are remarkable in terms of human health. Among these, palm oil, which is mainly associated with cardiovascular disease (CVD), is a vegetable oil type that is widely used in the food industry. Moreover, the fractionation of palm oil has become quite common in the food industry when compared to other culinary oils and fats. Fractional crystallization, which has been recently regarded as an alternative to hydrogenization and interesterification methods, has become more popular in edible oil technology, even though it is an ancient method. The main fractions of palm oil are palm olein and palm stearin. Palm oil fractions, which have some pros and cons, are used in edible oils, such as margarine/shortening, as well as bread and cake-like pastry production. Since the fatty acid composition of palm oil, palm kernel oil, and their fractions is different, each type of oil needs to be evaluated separately with regards to their CVD effects and food preparation applications. However, the effects of the fractionation method and the fractional palm oil produced on health are controversial in the literature. In this review, the use of palm oil produced via the fractional crystallization method in the food industry and its potential CVD effects were evaluated.

Oleogel-based emulsions: Concepts, structuring agents, and applications in food.

This review discusses the application of oleogel technology in emulsified systems. In these systems of mimetic fats, water-in-oil or oil-in-water emulsions can be obtained, but, here, we cover emulsions with an oil continuous phase in detail. Depending on the percentage of water added to the oleogels, systems with different textures and rheological properties can be developed. These properties are affected by the characteristics and concentration of the added components and emulsion preparation methods. In addition, some gelators exhibit interfacial properties, resulting in more stable emulsions than those of conventional emulsions. Oleogel-based emulsion are differentiated by continuous and dispersed phases and the structuring/emulsification components. Crucially, these emulsions could be applied by the food industry for preparing, for example, meat products and margarines, as well as by the cosmetics industry. We present the different processes of emulsion elaboration, the main gelators used, the influence of the water content on the structuring of water-in-oleogel emulsions, and the structuring mechanisms (Pickering, network, and combined Pickering and network stabilization). Finally, we highlight the applications of these systems as alternatives for reducing processed food lipid content and saturated fat levels.

Non-targeted detection of butter adulteration using pointwise UHPLC-ELSD and UHPLC-UV fingerprints with chemometrics.

A non-targeted chemometric method was devised to detect possible butter adulteration without prior knowledge of the adulterant and marker compounds. Nine common edible oils including vegetable oils, animal fats and margarines were selected as potential adulterants to build a unified classification model. The samples were analyzed using the high-performance liquid chromatography hyphenated with an evaporative light scattering detector (UHPLC-ELSD) and an ultraviolet detector (UHPLC-UV), with the pointwise chromatograms instead of individual peaks for modelling. Both models achieved over 95% correct classification in external validation at the adulteration levels as low as 5% (w/w). The root mean squared errors of prediction (RMSEP) of the regression model were 0.9865 and 1.9080 for UHPLC-ELSD and UHPLC-UV, respectively. Non-targeted chemometrics analyses based on pointwise chromatographic profiles could be valuable for detecting adulterated butter.

Innovative smart and biodegradable packaging for margarine based on a nano composite polylactic acid/lycopene film.

In this study, polylactic acid (PLA)/titanium dioxide/lycopene (PLA/TiO2/Lyc) nano-composite film was prepared. The morphology and mechanical properties of the film were studied by SEM and texture analyser. Results showed that lycopene and TiO2 nanoparticles were distributed in the film matrix uniformly, TiO2 and lycopene increased the mechanical properties of PLA film. The PLA/TiO2/Lyc film was used to package margarine. The effect of PLA/TiO2/Lyc film, time and temperature of storage on the qualitative features of margarine were studied. Also the colour properties of PLA/TiO2/Lyc film were studied during storage period. Oxidative features (antioxidant activity, acidity number, peroxide value and thiobarbituric acid value) of margarine showed that the quality features of margarine decreased during storage, but the PLA/TiO2/Lyc film controled the oxidative factors and increased the margarine shelf life significantly (P < .05). Results also showed that the PLA/TiO2/Lyc film colour changed from red to light yellow during storage. With increasing margarine storage time, the film colour index a decreased (red colour diminished) while b increased (yellow colour increased). There were good relations between colour changes of film and oxidative parameters of margarine and storage time and storage temperature. Thus PLA/TiO2/Lyc film can be used as a visual indicator of the oxidation variations during storage of packaged margarine.

Determination of 3-monochloropropanediol esters and glycidyl esters in fatty matrices by ultra-high performance liquid chromatography-tandem mass spectrometry.

The development and validation of a method for the analysis of traces of 3-monochloropropanediol (3-MCPD) esters (19) and glycidyl esters (7) of fatty acids in vegetable oils, margarine, biscuits and croissants was performed. An extraction method based on the use of solvents (tert­butyl methyl ether (20% ethyl acetate, v/v)) was carried out and cleaning of the extract with a mixture of sorbents (Si-SAX, PSA and Z-sep+) was optimized for the elimination of fatty interferents. The analysis of the targeted compounds was carried out by ultra-high-performance liquid chromatography coupled to tandem mass spectrometry, using a triple quadrupole analyzer (UHPLC-MS/MS-QqQ). The validation of the method provided trueness values between 72 and 118% and precision lower than 20%. The limits of quantification ranged from 0.01 to 0.1 mg kg-1, which were below the current legal limits. Twenty samples of vegetable oils as well of 4 samples of margarine, biscuits and croissants were analyzed. Six out of the 24 samples (25%) exceeded the limits set by European legislation, and a maximum contamination of 3-MCPD esters at 2.52 mg kg-1 was obtained in a sample of corn oil (being 1-myristoyl-3-MCPD the compound detected at the highest concentration). A maximum concentration of glycidyl esters at 7.84 mg kg-1 was determined in a soybean oil sample (glycidyl linoleate as the main compound). Only one sample of olive oil exceeded the maximum allowable limit for 3-MCPD esters with a value of 1.72 mg kg-1, expressed as 3-MCPD.

Properties of margarines prepared from soybean oil oleogels with mixtures of candelilla wax and beeswax.

The aim of this study was to examine the physical properties of margarines prepared from oleogels with binary mixtures of candelilla wax (CDW) and beeswax (BW) in soybean oil. Some of the margarines made from oleogels with mixtures of CDW and BW had higher firmness than those made with one wax. For example, a 3% wax margarine made with 25% CDW and 75% BW had significantly higher firmness (0.97 N) than those with 100% CDW (0.59 N) and with 100% BW (0.11 N). Differential scanning calorimetry (DSC) and solid fat content (SFC) analyses revealed eutectic melting properties for binary wax margarines, which may be desirable since wax oleogel-based margarines often have higher melting points than conventional margarines. For example, the major melting point of 3% wax margarine made with 50% CDW and 50% BW was 43.85 °C, while for margarines made with 100% CDW or 100% BW, the melting points were at 46.00% and 47.61 °C, respectively. SFC was lowest for margarines with 50 or 75% BW; for example, 3% wax margarine with 25% CDW and 75% BW had 0.72% SFC at 40 °C while those with 100% CDW and 100% BW had 1.19 and 1.13% SFC, respectively. However, dropping point constantly decreased with increasing BW ratios. This study demonstrated that by mixing two waxes, the firmness of oleogel-based margarines could be increased, and the melting point could be tailored by the ratio of two waxes. PRACTICAL APPLICATION: This study demonstrated that firmness and melting properties of margarines prepared from wax-oleogels can be improved by mixing two waxes, making their practical application more feasible. Firmness of margarines prepared with oleogels of binary mixtures of candelilla wax and beeswax were higher than those with pure waxes. The melting point of wax oleogel-based margarines was decreased by use of binary mixtures of candelilla wax and beeswax.

Preparation and characterization of oleogel emulsions: A comparative study between the use of recovered and commercial sunflower waxes as structuring agent.

The objective of this study was to evaluate the capacity of recovered sunflower waxes (RW) to be used as a structuring agent of oleogel emulsions in comparison with commercial sunflower waxes (CW). RW were recovered from filter cake with a simple hexane extraction procedure. For this purpose, oleogel-based emulsions were prepared using 2%, 3.5%, and 5% w/w wax in oleogel and characterized using several physicochemical techniques in order to evaluate the potential of these materials to develop products with functionality similar to commercial margarines. The total wax esters content of RW was similar to that of the CW and was mainly composed of wax esters with more than 44 carbon atoms (crystallizable waxes). Polarized light and scanning electron microscopy showed that RW produced emulsions with more intricate crystalline networks composed of smaller platelets than CW. The melting enthalpy was greater in CW emulsions than RW emulsions, which was in agreement with the thermal behavior found for CW and RW. The oil binding capacity of CW oleogel emulsions was higher than the RW ones, and this property improved with the increase in wax concentration. Likewise, the elastic behavior, as well as hardness and adhesiveness, increased with the wax content as a result of a greater amount of microstructural elements composing the network of these semisolid materials. The oleogel emulsions stability was monitored for 2 months at room temperature. The increase of CW concentration slowed down the coalescence process, but this behavior was not observed for RW emulsions. Obtained results demonstrated that RW oleogel emulsions have the potential to replace the functionality of soft spreadable products. PRACTICAL APPLICATION: Wax esters are organogelators that have been shown to successfully gel liquid oil at low concentrations. In this work, we are interested in evaluating the potential of sunflower waxes recovered from filter cake, a waste generated during refined oil production, to structure oil and produce oil-in-water emulsions with functionality similar to commercial margarines. With this, it is sought not only the development of healthier fats but also the use of wastes to generate more sustainable products.

Evaluation of the quality of local butters: A new approach based on Raman spectroscopy and supported by the classical pycnometer method.

In this study, the quality of the local Romanian butters was investigated using the classical pycnometer and optic microscopy methods, combined with Raman spectroscopy. We used a pool of 10 samples with different characteristics, and analyzed them by the three aforementioned methods. Pycnometric measurements showed a direct correlation between the fat content and the density values of the samples. Raman spectroscopy validated the results from the pycnometric measurements and the optical microscopy and indicated several other properties, such as protein content, hydration, saturation level of the polycarbonate chains, as well as the total cis isomer content and the type of arrangement preferred by the aliphatic chains (polymorphic transition). The methods employed in the present study have a strong potential to become analytical tools for the food industry and food safety agencies in order to assess the quality of butters and margarines, in a fast and cost-effective manner.

Effects of Heat Treatment on Lactone Content of Butter and Margarine.

The lactone content of butter, fermented butter, and margarine was compared using gas chromatography-mass spectrometry. The main lactones in butters and fermented butters consisted of δ-decalactone, δ-dodecalactone, δ-tetradecalactone, δ-hexadecalactone, and γ-dodecalactone. In contrast, the main lactones in margarines were δ-decalactone and δ-dodecalactone. The total lactone content in butters and fermented butters increased by approximately two-fold upon heat treatment, whereas, heat treatment did not affect the lactone content in margarine. The changes in lactone content caused by heat treatment were greater in fermented butters than in butters. These findings suggested that the fermentation process could increase lactone or lactone precursor content in butter.

Simultaneous Analysis of Epoxidized and Hydroperoxidized Triacylglycerols in Canola Oil and Margarine by LC-MS.

The progress of lipid oxidation in foods is evaluated by measuring the peroxides and their scission products. However, hydrogen abstraction-independent pathways are not considered by commonly applied methods despite the known reactivity of epoxides toward biomolecules. Herein, a novel liquid chromatography tandem-mass spectrometry method was developed to detect hydroperoxidized and epoxidized triacylglycerols (TAGs) without derivatization or hydrolyzation of food samples. Epoxidized TAGs could be detected in refined canola oil at concentrations of 96.8 ± 2.08 µM, while only 5.77 ± 0.04 µM hydroperoxidized TAGs could be determined. In contrast to canola oil, margarine was more resistant to lipid oxidation since generation of epoxidized TAGs could only be marginally enhanced from 21.7 ± 0.48 to 28.8 ± 0.64 µM in margarine after treatment at 180 °C for 60 min, as also reflected by a peroxide value of 0.80 ± 0.00 mequiv O2/kg, which remained unchanged. The new method allows the assessment of food safety by the simultaneous measurement of hydroperoxidized and epoxidized TAGs without hydrolysis and laborious sample preparation.

Development of a partitioned liquid-liquid extraction- dispersive solid phase extraction procedure followed by liquid chromatography-tandem mass spectrometry for analysis of 3-monochloropropane-1,2-diol diesters in edible oils.

A fast and effective method using a modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) approach which includes partitioned liquid-liquid extraction (PLLE) and dispersive solid phase extraction (dSPE) clean-up step for the determination of seven 3-monochloropropane-1,2-diol (3-MCPD) fatty acid diesters in vegetable oils is developed and validated according to the Food and Drug Administration (FDA) guidelines. Due to the complexity of the matrices, combination of silica based sorbents (Silica Strong Anion Exchange (Si-SAX), Supel™ QuE Z-Sep+ (Z-Sep+) and Primary Secondary Amine (PSA) were tested for lipid removal. The effect of several experimental factors on the efficiency of the extraction procedure was studied by a screening design 3422//16 and a response surface Doehlert design. The separation and determination was carried out by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). The method provided suitable linearity (r2 > 0.9960), precision (relative standard deviation (RSD) lower than 10%) and accuracy, in terms of recovery. The limits of detection (LOD) and limits of quantification (LOQ) ranged from 10 to 20 µg kg -1 and from 25 to 50 µg kg-1, respectively. The recoveries at three spiking levels of 100, 250, and 500 µg kg-1 were over the range of 71.4-122.9% with RSD lower than 13%. The method was successfully applied in edible oils and fatty food samples. The results provide valuable information to assess the risk of exposure to these foodborne contaminants.

A low trans margarine fat analog to beef tallow for healthier formulations: Optimization of enzymatic interesterification using soybean oil and fully hydrogenated palm oil.

The health hazard of tallow and partial hydrogenated oils is well known in margarine productions. For this, food manufactures are urged to develop novel alternatives for healthier margarine formulations. The highest interesterification degree acquired with lipase Lipozyme 435 standing out from other catalysts (solid acid, sodium hydroxide and methoxide) was applied to produce low trans margarine fat analogs to beef tallow (BT) with the blend of soybean oil (SO) and fully hydrogenated palm oil (FHPO) in a mass ratio of 4:3. Reaction parameters like enzyme dosage (4.2 wt%), temperature (95 °C) and time (245 min) were optimized using the Box-Behnken design. Regarding fatty acid profiles, triacylglycerol species, solid fat content, polymorphism, melting and crystallization behaviors, the resulting interesterified oil was characterized in comparison with BT, FHPO and the SO-FHPO blend so as to prove its potential in formulating low trans fat margarines because of desirable physicochemical properties and polymorphs.