Differential Scanning Calorimetry Analysis of Goat Fats: Comparison of Chemical Composition and Thermal Properties

The physical–chemical properties, fatty acid composition and thermal properties of goat subcutaneous (SF), tallow (TF) and intestinal (IF) fats were determined. SF differed from other fat types with respect to its lower melting (41.6 °C), lower saponification (190.3 mg KOH/g) and higher iodine (40.4) values as compared to those of other fats. Goat fat types contained palmitic acid (C_16:0), stearic acid (C_18:0), oleic acid (C_18:1ω9) and linoleic acid (C_18:2ω6) as the major components of the fatty acid composition (23.06–23.52, 22.95–39.03, 21.94–36.16 and 1.96–2.22%, respectively). A differential scanning calorimetry (DSC) study revealed that two characteristic peaks were detected in both crystallization and melting curves. Major peaks (T _peak) of TF and IF were similar and determined as 34.02–35.24 and 9.95–10.72 °C, respectively for the crystallization peaks and 15.11–18.26 and 50.70–52.76 °C, respectively for the melting peaks in the DSC curves; but those of SF (27.14 and 4.36 °C for crystallization peaks and 8.39 and 44.93 °C for melting peaks) differed remarkably from those of other fat types.     

Kinetics of Melt Crystallization of a Sunflower Oil‐Based Polyunsaturated Fatty Acid Mixture

Important parameters like supercooling and cooling rates affecting the melt crystallization of a polyunsaturated fatty acid (PUFA) mixture obtained from sunflower oil were investigated and compared via high‐resolution polarized‐light microscopy. PUFA was thermally characterized in a differential scanning calorimeter and the significant liquid‐solid‐phase transition temperatures determined were then implemented in the development of specific temperature profiles. Analyzed between two glass slides, induction times were found to decrease with low crystallization temperatures and the number of nuclei per unit area increased with higher supercooling and cooling rates. A comparison between the linear crystal growth rates of pure standards of each of the main fatty acids present in the PUFA mixture and the PUFA mixture itself indicated that the latter is much slower than that of each of its pure components.     

A Comprehensive Evaluation of the Melting Points of Fatty Acids and Esters Determined by Differential Scanning Calorimetry

The melting point is one of the most important physical properties of a chemical compound and it plays a significant role in determining possible applications. For fatty acid esters the melting point is essential for a variety of food and non-food applications, the latter including biodiesel and its cold-flow properties. In this work, the melting points of fatty acids and esters (methyl, ethyl, propyl, butyl) in the C₈–C₂₄ range were determined by differential scanning calorimetry (DSC), many of which for the first time. Data for triacylglycerols as well as ricinoleic acid and its methyl and ethyl esters were also acquired. For some compounds whose melting points have been previously reported, data discrepancies exist and a comprehensive determination by DSC has not been available. Variations in the present data up to several °C compared to data in prior literature were observed. The melting points of some methyl-branched iso- and anteiso-acids and esters were also determined. Previously unreported systematic effects of compound structure on melting point are presented, including those for ω-9 monounsaturated fatty acids and esters as well as for methyl-branched iso and anteiso fatty acids and esters. The melting point of a pure fatty acid or ester as determined by DSC can vary up to approximately 1 °C. Other thermal data, including heat flow and melting onset temperatures are briefly discussed. Product names are necessary to report factually on available data; however, the USDA neither guarantees nor warrants the standard of the product, and the use of the name by USDA implies no approval of the product to the exclusion of others that may also be suitable.     

Determination and Comparison of Equilibrium Data of Various Plant‐Based Fatty Acid Mixtures

Multistage melt crystallization of a variety of plant‐based polyunsaturated fatty acid (PUFA) mixtures was conducted to obtain an overview on their liquid‐solid equilibrium behavior. Crystal fraction and mother liquor samples were analyzed at every stage. Phase behavior diagrams at low saturated fatty acid concentrations were investigated in detail as they are of significant technical relevance with respect to efficient depletion of the saturated content from the samples. A high oleic acid content in the PUFA mixtures led to difficulties in depleting the mother liquor from the saturated content by melt crystallization. Thermograms from the differential scanning calorimetry were supplemented with illustrations which allow a novel interpretation of results and verification of conclusions.     

Preparation and Characterization of Oil Rich in Odd Chain Fatty Acids from Rhodococcus opacus PD630

Odd-chain fatty acids (OCFA) are widely used in pharmaceutical and food industries, as well as the chemical industry. In this study, oil rich in OCFA was produced by Rhodococcus opacus PD630, and 1-propanol in combination with glucose was used as the carbon and energy source. Oil was extracted by the subcritical extraction system. Gas chromatography (GC), ultra-performance liquid chromatography-mass spectrometry (UPLC-MS), and differential scanning calorimetry (DSC) were used to evaluate the fatty acids composition, triacylglycerol (TAG) molecular species, and thermal properties, respectively. It was found that the content of OCFA reached 68.15%, where pentadecanoic acid (7.74%), heptadecanoic acid (18.20%), and heptadecenoic acid (42.71%) were the dominant OCFA. The most abundant TAG were HePaHa (15.82%), HePHa (11.42%), HePaHe (9.68%), HeHaHa (9.62%), HePaO (8.26%), and HePPa (8.00%). In terms of thermal profiles, recrystallization was detected in the oil rich in OCFA. Above all, these findings greatly extend the utilization of the microbial oil rich in OCFA, and they may have a significant impact on the future development of the microbial oil industry.     

The Discrepancy of Fatty Acid Composition of Astaxanthin Esters and Total Fatty Acids in Photoautotrophic and Heterotrophic Chlorella zofingiensis

Chlorella zofingiensis has great potential for astaxanthin and fatty acid production. This study investigated the accumulation of astaxanthin and total fatty acids (TFA), the fatty acid compositions of astaxanthin esters and TFA in photoautotrophic and heterotrophic C. zofingiensis, respectively. The results displayed that in photoautotrophic cells, 18:3 was the most predominant fatty acid, followed by 16:0, 18:2, and 18:1, while astaxanthin mono-esters (mono-AE) contained only 16:0 and 18:0, and astaxanthin di-esters (di-AE) contained 16:0 mostly, followed by 18:1, 18:0, 18:2, and 18:3. C. zofingiensis accumulated the highest level of astaxanthin and TFA under heterotrophic conditions fed with 30 g L⁻¹ glucose. The percentage of 18:1 in TFA, mono-AE, and di-AE increased from 10.05%, 0%, and 17.76% to 35.80%, 14.84%, and 50.12%, respectively; in contrast, the percentages of 18:3 in TFA and di-AE were observed to decrease from 40.42% and 7.59% to 9.56% and 1.30%, respectively, in comparison with those in photoautotrophic ones. The RNA sequencing (RNA-seq) results showed that the expressions of the genes in astaxanthin and fatty acid biosynthetic pathways were increased under this heterotrophic condition. These results indicated differential accumulation of AE and TFA, especially fatty acid compositions of TFA and AE in photoautotrophic and heterotrophic cells, suggesting a positive correlation between astaxanthin and fatty acid biosynthesis.     

Thermal stability of gelatin gels: Effect of preparation conditions on the activation energy barrier to melting

10, 20, and 40 wt.% aqueous gelatin gels were prepared under isothermal (annealing at 15, 20, and 25 °C for 15 to 120 min) and nonisothermal (cooling at 1 °C min⁻¹) conditions. Isoconversional kinetic analysis of DSC data on gel melting (gel-sol transition) of all types of gels revealed significant variations in the activation energy throughout the process. Activation energy barrier to melting of isothermally prepared gels was in the range 160-190 kJ mol⁻¹ and found to increase with increasing the annealing temperature that was the major effect discovered. Activation energy barrier to melting of nonisothermally prepared gels was determined to be around 120-140 kJ mol⁻¹ and increase with increasing the concentration. Local reversibility of the gel melting was demonstrated by using temperature modulated DSC.     

Thermal behavior of prospective hydroxy acid grease thickeners

Melting points and heats of fusion were determined for 13 hydroxy acids and their lithium salts with chain lengths ranging from 14 to 24 carbons. Included were hydroxy acids prepared from two unusual plant sources,Lesquerella sp. andCrambe abyssinica. Upper melting point temperatures, transition entropies, and heat capacity changes of the lithium salts on heating and cooling suggest that many of the salts, particularly those of 14-hydroxyeicosanoic and 9(10)-hydroxystearic acids, would perform satisfactorily as gelling agents in the production of lubricating greases. The mention of firm names or trade products does not imply that they are endorsed or recommended by the U.S. Department of Agriculture over other firms or similar products not mentioned. metal salts of unsubstituted fatty acids, which also can serve as grease thickeners.     

Thermal and Phase Change Material Properties of Comb-Like Polyacrylic Acid-Grafted-Fatty Alcohols

Poly(acrylic acid)-graft-fatty alcohol are synthesized from the esterification of polyacrylic acid with octadecanol and docosanol. The characterization of poly(acrylic acid)-graft-fatty alcohol was performed by attenuated total reflection–Fourier transform infrared spectroscopy. The thermal stability performances and phase change behaviors of poly(acrylic acid)-graft-fatty alcohol were examined by using thermogravimetric analysis system and differential scanning calorimetry. The results indicate that the poly(acrylic acid)-graft-fatty alcohol polymeric phase change materials possess good phase change properties and provide a suitable working temperature range. The heating process phase change enthalpy is measured between 112 and 122?J g^?1, and the freezing process phase change enthalpy is found between 118 and 126?J g^?1. The decomposition of poly(acrylic acid)-graft-fatty alcohol polymeric phase change materials started at 177°C and reached a maximum of 380°C. All of the obtained poly(acrylic acid)-graft-fatty alcohol polymeric phase change materials improved latent heat storage capacity in comparison with the pristine poly(acrylic acid) polymer. With the obtained results we conclude that, these materials promise a great potential in thermal energy storage applications.     

Effects of Heating Conditions on the Thermal Denaturation of White Mushroom Suitable for Dehydration

White mushrooms suitable for drying are thermolabile materials. At present, the determination of thermal denaturation of dehydrated white mushroom mainly depends on the drying technology. To choose the appropriate dehydration technology for thermal analysis, differential scanning calorimetry (DSC) was used for determining the denaturing temperature range. White mushrooms at five different moisture content levels were chosen for the DSC tests. Five heating rates were used to observe the change of the denaturing ranges. Finally, the effects of short-term storage and instantaneous increases in temperature on the change of denaturing areas are discussed.     

Effects of Heating Conditions on the Thermal Denaturation of White Mushroom Suitable for Dehydration

Abstract

White mushrooms suitable for drying are thermolabile materials. At present, the determination of thermal denaturation of dehydrated white mushroom mainly depends on the drying technology. To choose the appropriate dehydration technology for thermal analysis, differential scanning calorimetry (DSC) was used for determining the denaturing temperature range. White mushrooms at five different moisture content levels were chosen for the DSC tests. Five heating rates were used to observe the change of the denaturing ranges. Finally, the effects of short-term storage and instantaneous increases in temperature on the change of denaturing areas are discussed.     

Crystallization Behavior of Fatty Acid Methyl Esters

Biodiesel from most agricultural feedstocks has flow properties that are prone to startup and operability problems during cold weather. Biodiesel from soybean oil is generally a mixture of long-chain fatty acid alkyl esters composed of 0.15–0.20 mass fraction saturated esters (melting point [MP] ≫ 0 °C) mixed with unsaturated esters (MP < 0 °C). This work investigates the crystallization properties of two saturated fatty acid methyl esters (FAME) commonly found in biodiesel from soybean oil. Differential scanning calorimetry (DSC) heating and cooling scans of methyl palmitate (MeC16), methyl stearate (MeC18) and methyl oleate (MeC18:1) in pure form were analyzed. Crystallization behavior in ternary FAME mixtures was inferred by the application of thermodynamic models based on ideal solution and freezing-point depression theories. Activity coefficients for MeC16 and MeC18 in MeC18:1 solvent were determined by analyzing DSC cooling curves for binary FAME mixtures. Eutectic points were predicted by both models. Crystallization onset temperatures inferred from freezing point depression theory were more accurate than those for ideal solutions with respect to a direct DSC cooling curve analysis of corresponding ternary mixtures. This work shows that the crystallization onset temperature (cloud point) of biodiesel may be predicted by freezing-point depression theory if the activity coefficients of the component FAME are known. The use of trade, firm, or corporation names in this publication is for the information and convenience of the reader. Such use does not constitute an official endorsement or approval by USDA or ARS of any product or service to the exclusion of others that may be suitable.     

Fatty Acids in Liver,Muscle and Gonad of three Tropical Rays including Non-Methylene-Interrupted Dienoic Fatty Acids

Scientific investigation of lipids in Elasmobranchs has been conducted mainly on shark species. Because rays seem to be neglected, this study was performed to examine the complete fatty acid (FA) composition with a particular interest for long-chain polyunsaturated FA (PUFA) content in different tissues of three ray species including parts usually discarded. The total FA and PUFA profiles of total lipids were determined in muscle, liver, and gonad of Rhinobatos cemiculus, Rhinoptera marginata, and Dasyatis marmorata, the most often caught ray species from the East Tropical Atlantic Ocean. Fifty FA were characterized as methyl esters and N-acyl pyrrolidides by gas chromatography/mass spectrometry, showing significant levels of 20:5n-3 (EPA) (up to 5.3%) and 22:5n-3 (DPA) (up to 7.3%), high levels of 20:4n-6 arachidonic (ARA) (4.8–8.6% of total FA) and 22:6n-3 (DHA) (up to 20.0%). The results show that muscle, liver and gonad of rays can provide high amounts of essential PUFA, specially DHA, for direct human nutrition or the food processing industry. High proportions of DHA were particularly found in all samples of R. cemiculus (11.6–20.0%), and in muscle and liver of D. marmorata (11.1–16.1%). Regarding the high amounts of (n-3) PUFA, this study shows that these rays deserve a better up-grading, including the normally discarded parts, and describes the occurrence of unusual NMID FA in all tissues studied. Five non-methylene-interrupted dienoic fatty acids (NMID FA) (0–3.4%) were reported, including previously known isomers, namely 20:2 Δ7,13, 20:2 Δ7,15, 22:2 Δ7,13, 22:2 Δ7,15, and new 22:2 Δ6,14. These acids are quite unusual in fish and unprecedented in rays. The 22:2 Δ6,14 acid occurred in gonads of male specimens of R. cemiculus at 2.9%.     

Determination of Thermal Properties and Morphology of Eucalyptus Wood Residue Filled High Density Polyethylene Composites

Thermal behaviors of eucalyptus wood residue (EWR) filled recycled high density polyethylene (HDPE) composites have been measured applying the thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Morphology of the materials was also studied using scanning electron microscope (SEM). Addition of the EWR into the recycled HDPE matrix reduced the starting of degradation temperature. EWR filled recycled HDPE had two main decomposition peaks, one for EWR around 350 °C and one for recycled HDPE around 460 °C. Addition of EWR did not affect the melting temperature of the recycled HDPE. Morphological study showed that addition of coupling agent improved the compatibility between wood residue and recycled HDPE.     

The Effects of Thermal Treatment on Associations between Fatty Acids and Montmorillonite

The sorption from CCl₄ solutions of acetic, lauric and stearic acids by montmorillonites saturated with H, Li, Na, K, Cs, Ca, Mg, Cu, Al and Fe, was studied by IR and X-ray methods combined with various thermal treatments. Two distinct species were detected in the clay phase, the carboxylic acid (RCOOH) and the carboxylate anion (RCOO⁻). The ratios of the two sorbed species were found to be dependent both on the nature of the exchangeable cation and on the chain length of the acid. In Al⁻, Fe⁻ and Cu—montmorillonites, the ionic species predominates whereas in Cs—montmorillonite the acidic species predominates. Stearic acid shows the highest tendency to dissociate. The following associations were identified as occurring in the interlayer space: (I) and (II) — linkages between COOH group and oxygen sheet of silicate layer or with hydrophobic structured water; (III) — linkage between a COOH group and an exchangeable cation through a “water bridge”; (IV) — direct linkage between a COOH group and an exchangeable cation; (V) — linkage between a COO⁻ group and an exchangeable cation through a “water bridge” and (VI) — direct linkage between a COO⁻ group and an exchangeable cation. Although several types of associations are associated with every homoionic montmorillonite, some are more predominant. Thus, with Cs, association (I) predominates. With Li, Ca and Mg, association (III) predominates and is transformed to (IV) after thermal dehydration; whereas with Na and K association (IV) appears in freshly prepared sample. Al, Fe and Cu—montmorillonites mainly produce association (V). This structure is transformed into (VI) in the case of Al—montmorillonite by stearic and lauric acids, only. In the case of Cu—montmorillonite, all the three acids are transformed into (VI), but at 200°C decarboxylation of lauric and stearic acids occur.     

The Role of Lipid Composition in the Sensory and Physical Properties of Lipsticks

The perception of lipstick texture upon application is a key driver of consumer satisfaction. However, formulators may only rely on the absence of knowledge about the relationship between ingredients and product sensory properties. Lipsticks are made of a complex anhydrous mixture that contains about 80% lipids (oils, waxes, and butters). The goal of this work was thus to investigate the combined effect of multiple lipid ingredients on the sensory and physical properties of a cosmetic product such as lipstick. To this end, we first analyzed a typical lipstick formula and its related categories of ingredients. This allowed us to create a simplified, yet realistic lipstick system. Based on this, we formulated 36 lipsticks varying in oil and butter composition according to three mixture designs. All products were evaluated by a panel of sensory experts—with a focus on the slipperiness and melting perception—and analyzed using texture measurements. The physical and sensory results both show that the oils had the strongest impact on the lipstick properties while the impact of the butter was negligible. Moreover, the perceived slipperiness of lipsticks was closely related to the viscosity of the oil mixture present in the formula (R² = 0.87). Further analyses of lipstick physicochemical properties by differential scanning calorimetry suggest that the nature and amount of oil influence the crystallization of butter and wax, which could explain the dominant impact of the oils on the sensory and mechanical properties of lipsticks.     

The Divergent Immunomodulatory Effects of Short Chain Fatty Acids and Medium Chain Fatty Acids

Fatty acids are derived from diet and fermentative processes by the intestinal flora. Two to five carbon chain fatty acids, termed short chain fatty acids (SCFA) are increasingly recognized to play a role in intestinal homeostasis. However, the characteristics of slightly longer 6 to 10 carbon, medium chain fatty acids (MCFA), derived primarily from diet, are less understood. Here, we demonstrated that SCFA and MCFA have divergent immunomodulatory propensities. SCFA down-attenuated host pro-inflammatory IL-1β, IL-6, and TNFα response predominantly through the TLR4 pathway, whereas MCFA augmented inflammation through TLR2. Butyric (C4) and decanoic (C10) acid displayed most potent modulatory effects within the SCFA and MCFA, respectively. Reduction in TRAF3, IRF3 and TRAF6 expression were observed with butyric acid. Decanoic acid induced up-regulation of GPR84 and PPARγ and altered HIF-1α/HIF-2α ratio. These variant immune characteristics of the fatty acids which differ by just several carbon atoms may be attributable to their origins, with SCFA being primarily endogenous and playing a physiological role, and MCFA exogenously from the diet.     

Thermal and morphological properties of main chain liquid crystalline polymers

Temperature modulated differential scanning calorimetry (TMDSC), variable heating rate DSC, and tapping atomic force microscopy (AFM) were used to study semi-crystalline liquid crystalline polymers (LCPs). Main chain LCPs included a random copolyester (Vectra® A950) and an azomethine alternating copolymer. For the azomethine LCP the TMDSC non-reversing signal detected broad exothermic transitions associated with melting and recrystallization as the slow DSC heating scan induced surprisingly large morphological changes. Non-isothermally crystallized Vectra® and some isothermally crystallized samples at lower temperatures exhibited different levels of DSC scan induced crystal reorganization. Such crystal metastability was also studied by variable heating rate DSC and an independent technique for estimating the melting point at very rapid heating rates. The TMDSC characterization of the scan induced crystal perfection in Vectra® was substantially different than for the other polymers studied. In most cases even though crystal perfection was occurring, no clear exotherm was detected in the non-reversing signal. High temperature annealing for long times resulted in degrees of crystal perfection which could be studied by DSC with minimal scan induced reorganization. High resolution tapping AFM was used to elucidate details of crystal morphology for mechanically oriented and non-oriented Vectra® before and after annealing. Structures resembling lamellae were found to be oriented perpendicular to the chain direction in the oriented Vectra®. In the non-oriented film broad and sometimes curved ‘lamellae’ were detected. They were about 1000 nm long and between 20 and 35 nm wide, with the width increasing slightly as a function of increased annealing time at 260 °C melt crystallization conditions. Substructure of the lamellae in both oriented and non-oriented Vectra® consisted of smaller stacked crystallites which are detected by AFM studies of these surfaces.     

Comparative Oxidative Stability of Fatty Acid Alkyl Esters by Accelerated Methods

Several fatty acid alkyl esters were subjected to accelerated methods of oxidation, including EN 14112 (Rancimat method) and pressurized differential scanning calorimetry (PDSC). Structural trends elucidated from both methods that improved oxidative stability included decreasing the number of double bonds, introduction of trans as opposed to cis unsaturation, location of unsaturation closer to the ester head group, and elimination of hydroxyl groups. Also noticed with EN 14112 was an improvement in oxidative stability when a larger ester head group was utilized. Methyl esters that contained ten or less carbons in the fatty acid backbone were unacceptable for analysis at 110 °C (EN 14112) due to excessive sample evaporation. With respect to PDSC, a correlation was noticed in which the oxidation onset temperature (OT) of saturated fatty esters increased with decreasing molecular weight (R ² 0.7328). In the case of the monounsaturates, a very strong inverse correlation was detected between molecular weight and OT (R ² 0.9988), which was in agreement with EN 14112. Lastly, a strong direct correlation (R ² 0.8759) was elucidated between OT and oil stability index (OSI, EN 14112, 80 °C). The correlation was not as strong (R ² 0.5852) between OSI obtained at 110 °C and OT. Disclaimer: Product names are necessary to report factually on available data; however, the USDA neither guarantees nor warrants the standard of the product, and the use of the name by USDA implies no approval of the product to the exclusion of others that may also be suitable.