Differential scanning calorimetric analysis for monitoring the oxidation of heated oils

A simple and reliable differential scanning calorimetric (DSC) method was developed for monitoring the oxidation in heated oils. Three different types of edible oils, namely, corn oil (CO), refined, bleached and deodorised palm olein (RBDPO) and soybean oil (SO) were used in this study. The DSC method was based on the cooling thermogram of oil samples at a scanning rate of 1°C/min from −30 to −85°C. The cooling thermogram of oil showed a well-defined single crystallisation peak. Two DSC parameters of this single crystallisation peak, namely peak temperature and enthalpy were determined. In addition to the DSC method, the deterioration of heated oils was also quantified by means of seven chemical methods. A statistical comparative study was carried out on the DSC and chemical methods. The results show that there is good correlation between the DSC method and other standard chemical methods. In conclusion, the DSC method offers an alternative for the monitoring of the oxidation of heated oil due to its appreciable time-saving, use of small samples with minimal preparation, and absence of toxic chemicals.     

Differential scanning calorimetry thermal properties and oxidative stability indices of microwave heated extra virgin olive oils

BACKGROUND: The use of differential scanning calorimetry (DSC) for assessing the deterioration effect of microwave heating on vegetable oils, and on olive oils in particular, has been partially explored in literature. The aim of this work was to evaluate the potential of DSC to discriminate among microwaved extra virgin olive oils (EvOo from different olive cultivar and origin), according to changes on thermal properties (upon cooling and heating) and traditional oxidative stability indices (peroxide, p‐anisidine and TOTOX values). RESULTS: An elevated value of lipid oxidation was reached by the most unsaturated EvOo sample (9.5% of linoleic acid) at 6 min of microwave treatment. Free acidity significantly increased (0.42%) only for the oil sample with the highest water content (874 mg kg^?1 oil) at the longest time of treatment. Crystallisation enthalpies significantly decreased and the major exothermic peak shifted towards lower temperature, leading to enlargement of the transition range in all samples due to the formation of weak and mixed crystals among triacylglycerols and lipid degradation products. On the contrary, thermal properties upon heating appeared to similarly vary among samples. CONCLUSIONS: The analysis of DSC thermal properties upon cooling seemed to clearly discriminate among different EvOo samples after microwaving. The relation between changes of thermal properties and oxidation parameters should be further studied using additional oxidative stability indices on a larger set of oil samples, due to the complexity of EvOo composition. Copyright © 2010 Society of Chemical Industry     

Microwave heating of different vegetable oils: Relation between chemical and thermal parameters

Changes of DSC profiles and thermal properties (upon cooling and heating) were evaluated at different times of microwave heating on refined peanut (Pto), high oleic sunflower (HOSo) and canola (Co) oils and compared to the results obtained for standard chemical indices (free fatty acids, peroxide, p-anisidine, OSI time) and antioxidant capacity (Trolox equivalent antioxidant capacity). Co was more extensively oxidised by microwave heating than the other two oils probably as a consequence of the higher degree of unsaturation, even though it showed a higher antioxidant capacity. Microwave heating also induced alterations in both cooling and heating profiles of the oils, mainly in Pto and Co, shifting phase transitions towards lower temperature and enlarging temperature range. High statistical correlation coefficients were obtained among thermal properties both upon cooling and heating and chemical indices (i.e. free fatty acids and p-anisidine values). The analysis of both cooling and heating profiles and related thermal properties appears to be a valuable tool to assess different degrees of lipid thermoxidation induced by microwave in vegetable oils being also very useful for the ready-to-eat food sector and the vegetable oil industry.     

Chemical and thermal characterization of Tunisian extra virgin olive oil from Chetoui and Chemlali cultivars and different geographical origin

Application of differential scanning calorimetry (DSC) to discriminate among extra virgin olive oils on the basis of cultivar–environment interaction was preliminary evaluated on Tunisian samples from two varieties (Chetoui and Chemlali) and different geographical origin relating thermal properties obtained by cooling and heating thermograms to chemical composition. Higher content of triunsaturated triacylglycerols and oleic acid and lower amount of palmitic acid were detected in Chetoui samples in comparison with Chemlali oils. Cooling thermograms exhibited two well distinguishable exothermic peaks in all samples; the major event at lowest temperature was taller and sharper in Chetoui samples whereas the other peaking at highest temperature was more evident for Chemlali oils. Crystallization enthalpy did not account for the differences observed in chemical composition between the two cultivars. On the contrary, T _on and T _off of crystallization were found to significantly differ according to the compositional differences due to cultivars and geographical provenience interaction. Heating profiles exhibited a minor exothermic peak followed by multiple endothermic events and appeared also distinctive of oil samples from two cultivars. All thermal properties obtained by the analysis of heating thermograms significantly differed among oil samples from different geographical provenience. The application of DSC appeared useful to differentiate samples of different cultivars and/or geographical proveniences.     

Microwave Heating Effects on Relative Stabilities of Tocopherols in Oils

The relative stabilities of individual tocopherols during microwave heating were investigated in fatty acid esters and tocopherol-stripped vegetable oils. The rate of tocopherol loss during heating was less from the highly unsaturated ethyl esters or vegetable oils than from ethyl laurate or olive oil. However, changes in chemical properties of the substrates depended on degree of unsaturation of esters and oils. The stability of tocopherols during microwave heating was δ > β > γ > α, and the order did not change with differences in the type of ethyl esters of fatty acids or oils.     

Characteristics of hemp (Cannabis sativa L.) seed oil

Characteristics of oil extracted from hempseeds subjected to microwave treatments were evaluated. Microwave treatment improved oil yield, increased carotenoid and other pigment contents and decreased p-anisidine value without significant changes in other properties. Hempseed oil showed absorbance in the UV-B and UV-C ranges with potential for use as a broad spectrum UV protectant. β-Tocopherol concentrations increased, while the major tocopherol, γ-tocopherol, and fatty acid composition of the oil were unaffected by microwave treatment of hempseed. Hempseed oil showed high kinetic stability during heating and cooling, as characterized by differential scanning calorimetry (DSC). Microwave treatment shifted the melting range of oils to lower temperatures and increased oxidation temperatures, suggesting increased protective effect upon heating.     

Development of a green innovative semi-industrial scale pilot combined microwave heating and centrifugal force to extract essential oils and phenolic compounds from orange peels

A new process for extraction of essential oils from orange peels (Citrus sinensis L.) using microwave and centrifugal (MW/C) force was studied. MW/C is a combination of microwave heating to explode the internal cells of biological material, and centrifugation to intensify diffusion, collection and separation of compounds of interest. MW/C is performed at atmospheric pressure with an injection of water vapor. A detailed study concerning optimization of different operating parameters like microwave power density and centrifugation was performed. MW/C has been compared to the hydrodistillation method. In addition of essential oils collection, in the aqueous phase several phenolic compounds can be obtained and valorized. Influence of the two main parameters was discussed first on essential oils and, in second part, on phenolic compounds recovery. The new combined MW/C process provided reduction in the extraction time compared to hydrodistillation method, with an advantage to collect in a same experiment volatile and nonvolatile compounds with high quality.Industrial relevanceThis work was carried out thanks to the investment of IFTS France, an international technical center worldwide known in the field of solid-fluid separations. Considering the huge amount of plant extracts this new combined system using microwave and centrifugal (MW/C) force may be suitable for scaling up. The results of this investigation on pilot reactors pave the way for the design of an industrial device.     

微波加热对食用油品质及脂肪酸成分的影响

研究微波加热对食用油品质及脂肪酸成分影响,为家庭健康烹调提供理论依据。用家用微波炉的不同加热档位,对菜籽油、大豆油等8种常用食用油加热不同时间,用滴定法测定加热后油脂的酸价和过氧化值,GC-MS测定油脂的脂肪酸成分,并以这些指标评价微波加热对食用油品质的影响。在实验所用加热条件下,8种食用油的酸价和脂肪酸成分均未发生明显改变。不同食用油的过氧化值变化曲线有所不同,菜籽油、大豆油、花生油、芝麻油、调和油的过氧化值随着微波功率和时间增加而上升,玉米油、橄榄油和葵花籽油的过氧化值随着微波功率和时间增加先上升后下降。微波加热虽然改变了食用油的过氧化值,但酸价尚未发生改变,认为油脂尚未发生酸败,微波加热也没有破坏食用油原有的脂肪酸组成。从微波加热对食用油的品质和脂肪酸成分影响的结果看,可以认为微波加热是日常生活中安全和健康的加热方式。     

Effect of Extraction Method on the Oxidative Stability of Camelina Seed Oil Studied by Differential Scanning Calorimetry

Camelina seed is a new alternative omega‐3 source attracting growing interest. However, it is susceptible to oxidation due to its high omega‐3 content. The objective of this study was to improve the oxidative stability of the camelina seed oil at the extraction stage in order to eliminate or minimize the use of additive antioxidants. Camelina seed oil extracts were enriched in terms of natural antioxidants using ethanol‐modified supercritical carbon dioxide (SC‐CO₂) extraction. Oxidative stability of the camelina seed oils extracted by ethanol modified SC‐CO₂ was studied by differential scanning calorimeter (DSC), and compared with cold press, hexane, and SC‐CO₂ methods. Nonisothermal oxidation kinetics of the oils obtained by different extraction methods were studied by DSC at varying heating rates (2.5, 5, 10, and 15 ° C/min). Increasing ethanol level in the ethanol‐modified SC‐CO₂ increased the oxidative stability. Based on oxidation onset temperatures (T_on), SC‐CO₂ containing 10% ethanol yielded the most stable oil. Oxidative stability depended on the type and content of the polar fractions, namely, phenolic compounds and phospholipids. Phenolic compounds acted as natural antioxidants, whereas increased phospholipid contents decreased the stability. Study has shown that the oxidative stability of the oils can be improved at the extraction stage and this may eliminate the need for additive antioxidants.     

不同物理法提取高温大豆粕中蛋白的比较研究

比较了加热、均质、超声和微波4种物理手段对提取高温大豆粕中大豆蛋白的辅助作用,并对不同方法提取的蛋白进行了聚丙烯酰胺凝胶电泳(SDS-PAGE)、粒度分布、相对分子质量分布及热性质分析.研究发现120 ℃(0.1 MPa,20 min)热处理对大豆蛋白的提取效果最好,蛋白浸出率可达65.58%.SDS-PAGE、凝胶渗透色谱(GPC)和粒度分布结果显示,加热、超声和微波处理所得蛋白提取物为高相对分子质量聚集体,但除微波处理外,其分子粒径也有所减小;均质可使蛋白提取物的相对分子质量、粒径减小.差示量热扫描(DSC)结果表明,均质处理所得提取物尚有吸热峰存在,而其他手段处理所得提取物已完全变性.     

Antimicrobial effects of selected plant essential oils on the growth of a Pseudomonas putida strain isolated from meat

Dielectric properties of beef biceps femoris muscle were recorded during heating (5-85°C) to assess their linkage to phase changes monitored by differential scanning calorimetry (DSC) and rheology. DSC indicated endotherms between 56 and 81°C corresponding to denaturation of actin, collagen and myosin. Matching changes in dielectric properties (dielectric constant (ε') and loss factor (ε″)) were noted at radio and/or microwave frequencies though the nature of the change differed depending upon frequency. The main observation in ε' was an increase above 65-66°C, most likely due to fluid release on collagen denaturation. This fluid plus liquid from myosin denaturation most likely solvated ions freed during myosin denaturation which manifested as an ε″ increase. However, it must be noted that meat structural protein denaturation is compounded with physical shrinkage which can also influence dielectric properties. Rheological parameters of beef muscle heated from 5 to 85°C also displayed marked changes relating to structural protein denaturation.     

Combination of NMR and MRI Techniques for Non-invasive Assessment of Sea Cucumber (<Emphasis Type="Italic">Stichopus japonicas</Emphasis>) Tenderization During Low-Temperature Heating Process

The purpose of this study was to develop and test the combination of nuclear magnetic resonance (NMR) and magnetic resonance imaging (MRI) method to assess the proton changes of sea cucumber body wall during low-temperature heating process. NMR relaxometry and MRI measurements indicated a significant proton change in the internal structure for sea cucumber body wall when the heating temperature increased from 45 to 55 °C. Differential scanning calorimetry (DSC) analysis revealed that the denaturation temperature of sea cucumber body wall was in the range of 45–55 °C with an endothermic peak at 51 °C, which is in accordance with the result observed in NMR and MRI. Rheological study showed similar trend to the DSC thermogram. The band change in amide I region of Fourier transform infrared (FTIR) spectra indicated the decrease in α-helix content and possible formation of other secondary structures. Scanning electron microscopy (SEM) further confirmed that the low-temperature heating did induce microstructure changes. The analysis of the Ringer?s soluble fraction (RSF), enzyme-labile fraction (ELF), and total unaltered fraction (TUF) for sea cucumber body wall during low-temperature heating provided more detailed information on the cause of structure change observed in NMR and MRI. The NMR parameters were highly correlated with the rheology storage modulus (G′), relative enzymatic assay parameters, RSF, ELF, and TUF. All these results demonstrated that it could be possible to use NMR and MRI to assess sea cucumber tenderization during low-temperature heating process.     

Comparative studies of oxidative stability of edible oils by differential scanning calorimetry and oxidative stability index methods

A comparative study was conducted to determine the oxidative stability of twelve different edible oils with two different instruments: a differential scanning calorimeter and an oxidative stability index (OSI) instrument. The OSI instrument temperature was set at 110 °C. The differential scanning calorimetry (DSC) technique involved oxidation of oil samples in an oxygen-flow DSC cell. The DSC cell temperature was set at four different isothermal temperatures: 110, 120, 130 and 140 °C. A dramatic increase of evolved heat was observed with the appearance of a sharp exothermic curve during initiation of the oxidation reaction. The oxidative induction time (T₀) was automatically determined by extrapolation of the downward portion of the DSC oxidation curve to the time axis. There was a good correlation (P<0.0001) between the DSC T₀ and OSI values. The decrease in log₁₀ (T₀) with increasing DSC isothermal temperature was best fitted by a linear equation. DSC evidently provides a convenient way to determine the oxidative stability of various edible oils.     

微波加热与常规加热对植物油温度和氧化稳定性影响的对比

鉴于微波加热和常规外加热方式作用的内要机理完全不同,研究了两种加热方式对植物油温度和氧化稳定性影响的情况,发现植物油的温升速率受加热方式的影响较大,而其品质方面却没有太显著的关别。     

Microwave Energy Effects on Quality of Some Seed Oils

Effects of microwave heating were investigated on chemical properties of seed oils in relation to tocopherol contents. For assessing quality of oils (linseed, soybean, corn, olive, and palm) during microwave treatments, peroxide, thiobarbituric acid, carbonyl and anisidine values were determined. As the amount of polyunsaturated fatty acids in oils increased the index for the chemical properties increased. After 8-10 min heating the amount of tocopherols decreased substantially in linseed, olive and palm oils, whereas that in corn and soybean oils was still ca. 90%. Thus, the reduction in tocopherols in oils is not necessarily in agreement with chemical properties of the oils.     

加热方式对混合鱼糜凝胶特性的影响

本文以鲢鱼和鳕鱼为原料制成混合鱼糜,采用5种加热方式（水浴二段加热、微波加热、水浴微波联用、蒸汽加热、高压熟制）对混合鱼糜进行热处理。以鱼糜凝胶强度、持水力、白度以及质构特性为检测指标,通过SDS-PAGE凝胶电泳和扫描电镜检测方法,研究不同加热方式对混合鱼糜的凝胶特性的影响。结果表明:不同加热方式对混合鱼糜凝胶特性的影响不同。相比传统水浴二段加热,微波加热,蒸汽加热和高压熟制法,水浴微波联用法制备的混合鱼糜凝胶强度为2979.47 g·cm,持水力为94.33%,白度为83.75,硬度、弹性、胶粘性和咀嚼性显著提高（P<0.05）,扫描电镜图显示水浴微波联用法制备的鱼糜凝胶三维网状结构紧密,凝胶孔洞较小且表面平滑,结合SDS-PAGE凝胶电泳分析得出,加热会影响混合鱼糜凝胶中蛋白质成分降解,而水浴微波联用法制得的混合鱼糜凝胶的主要蛋白质成分保留较多。     

The suitability of DSC to obtain thermal reaction kinetics of whey proteins

Differential scanning calorimetry (DSC) provides a method for easily following the progress of reactions upon heating a material. Analysis techniques have been developed which allow reaction kinetics to be determined from thermograms; the two most frequently used, the Borchardt—Daniels and Kissinger methods, both rely on the assumption that only one reaction following Arrhenius kinetics takes place. These assumptions are not true for many systems, especially multi-component systems such as whey protein concentrates. The suitability of DSC for determining thermal reaction kinetics of whey protein concentrates was determined by applying both the Borchardt—Daniels and Kissinger methods to experimental and simulated DSC thermograms. Experimental results showed that kinetic parameters estimated by the Borchardt—Daniels method varied with protein concentration and/or scanning rate, showing that more than one reaction was taking place. The Kissinger method produced inaccurate estimates of the reaction order. Numerical simulations showed that the failure of the Kissinger method was due to sensitivity to random noise in the DSC power signal. The Borchardt—Daniels method was also affected by random noise, but to a lesser extent. It was concluded that the Kissinger method can only be used if the noise in the power signal can be decreased greatly. Kinetic parameters from the Borchardt—Daniels method should only be used with care.     

EFFECTS OF THERMAL AND ELECTROTHERMAL PRETREATMENTS ON HOT AIR DRYING RATE OF VEGETABLE TISSUE

Cylindrical samples of carrot, potato and yam were dried in a hot‐air dehydrator after preheating to 50C or 80C by three different heating methods (conventional, microwave and ohmic). The results showed that enhancement of drying rate increased with pretreatment temperature. Ohmic pretreatment increased the drying rate more than conventional and microwave heating. Desorption isotherms showed that in the low a_w range, desorption data of preheated and raw materials were similar. However, the isotherms of preheated samples shifted when a_w was high, which indicated that thermal pretreatments altered the structure, and apparently, the water distribution within these materials. For all samples, ohmic pretreatment showed stronger influences on isotherms than microwave heating, while the pretreatment effect of conventional heating was only observed for potato tissue.     

HAPTENIC CARBOHYDRATES AFFECT THE THERMAL DENATURATION OF SOYBEAN LECTIN

The effect of haptenic carbohydrates, N-acetyl-galactosamine and galactose, on soybean agglutinin (SBA) thermal denaturation was measured by differential scanning calorimetry (DSC) and batch heating in an oil bath. Thermodynamic parameters were determined by scanning from 30 to 11OC, at 1C/min. Lectin activity was measured by a hemagglutination test after heating at 80, 85, 90 and 95C for 5, 10, 15 and 20 min. Soybean lectin denaturation was an irreversible process with ΔH^±= 120 kcal/mol that was significantly reduced by carbohydrates, and it was a carbohydrate concentration dependent phenomenon. In addition, haptenic carbohydrates induced an increase of the T_max and T_tr of SBA denaturation when compared with soybean lectin solution alone. The loss of lectin activity was faster in absence of haptenic carbohydrates than those obtained from solutions with the specific sugars. It was concluded that haptenic sugars protected the SBA against denaturation.     

Effects of heating method and conditions on the quality attributes of black mulberry (Morus nigra) juice concentrate

Black mulberry juice was concentrated by different heating methods including conventional heating and microwave heating at different operational pressures (7.3, 38.5 and 100 kPa). The effects of each method of heating on the quality attributes of the concentrated juice were investigated. The final juice concentration of 42°Brix was achieved in 140, 120 and 95 min at 100, 38.5, and 7.3 kPa, respectively, by using a rotary evaporator. Applying microwave energy decreased the required times to 115, 95, and 60 min. The changes in anthocyanin, antioxidant, phenolic content, turbidity, pH value, and acidity during concentration were investigated. Results showed that the degradation of anthocyanins was more pronounced in rotary evaporation comparing to microwave heating method. The higher phenolic concentrations resulted in a smaller EC₅₀ value, which corresponds to a higher antioxidant activity of the mulberry extract.