Retardation of Crystallization of Diacylglycerol Oils Using Polyglycerol Fatty Acid Esters

Liquid oil containing high concentrations of diacylglycerols (DAG > 80 %, hereafter referred to as DAG-rich oil) is generally more likely to cause precipitation at chilled temperatures (clouding phenomena) than triacylglycerol-based oil. The clouding phenomena that occur during long-term storage of DAG-rich oil are unwanted in consumer products and therefore, must be prevented. In the present study, we attempted to retard precipitation by adding food emulsifiers, polyglycerol fatty acid esters (PGFE) containing different fatty acid moieties. DSC, polarized optical microscopy, and X-ray diffraction studies revealed that the addition of 0.2 % PGFE containing palmitic and oleic acid moieties very effectively retarded precipitation in the DAG-rich oil. To confirm these observations, we prepared a model DAG oil to mimic DAG-rich oil and examined the retardation behavior of high-melting DAG fractions using PGFE. The results are discussed in terms of the effects of PGFE additives on the pre-nucleation processes of high-melting fractions in DAG-rich oil.     

Formation and Microstructures of Whipped Oils Composed of Vegetable Oils and High-Melting Fat Crystals

This paper reports the experimental results of processes used for the formation of whipped oils composed of vegetable oils (salad oil) and high‐melting fat crystals [fully hydrogenated rapeseed oil rich in behenic acid (FHR‐B)]. No emulsifier was added to form this whipped oil. Microprobe FT‐IR spectroscopy, synchrotron radiation microbeam X‐ray diffraction (SR‐μ‐XRD), polarized optical microscopy, and differential scanning calorimetry (DSC) were employed to observe fine fat crystal particles of the most stable polymorph of β (β‐fat crystal), FHR‐B, and their adsorption at the air–oil surface before, during, and after the formation of the whipped oil. The results obtained revealed the following: (1) The preparation of an organogel composed of salad oil and small fibrous β‐fat crystals using a special tempering procedure was a prerequisite for forming whipped oil. (2) The β‐fat crystals were adsorbed at the air–oil surface to encapsulate the air bubbles during the formation process of whipped oil. (3) The values of overrun of the whipped oil reached >200 % after an aeration time of 30 min at 20 °C. (4) The SR‐μ‐XRD experiments demonstrated that the lamellar planes of the β‐fat crystals near the air–oil surface were arranged almost parallel to the air–oil surface plane. The present study provides the first evidence that tiny fat crystal particles may cause aeration in liquid oils without the addition of other whip‐assisting substances such as emulsifier crystals.     

Investigation of Oil and Protein Contents of Eight Sudanese Lagenaria siceraria Varieties

The composition of the oil and protein contents of eight Lagenaria siceraria varieties was characterized in order to evaluate their suitability as a source of edible oil and protein. The physicochemical properties and fatty acids of seed oils were determined. The oil yield ranged from 24.11 to 26.32 %. The refractive indices and relative densities of the oils fell within the narrow ranges of 1.464–1.468 and 0.857–0.907 g/cm³, respectively. The saponification value ranged from 158.48 to 179.52 mg KOH/g, unsaponifiable matter was between 0.749 and 0.937 %, and the peroxide values were lower than Codex values for vegetable oils. The principal fatty acids were linoleic (62.1–67.9 %), oleic (11.54–15.46 %), palmitic (12.13–14.03 %), and stearic (6.71–7.71 %) acids. Low linolenic acid levels were also observed (<1 %) within the range of 0.32–0.44 %. The major essential amino acids were arginine (2.04–3.77 g/100 g), leucine (1.245–1.726 g/100 g), phenylalanine (0.803–1.396 g/100 g), and lysine (0.921–1.383 g/100 g). The non‐essential amino acids were glutamic acid (2.5–4.37 g/100 g), aspartic acid (1.39–2.36 g/100 g), serine (0.69–1.19 g/100 g), glycine (0.79–1.37 g/100 g), alanine (0.72–1.37 g/100 g), and proline (0.63–1.02 g/100 g). Nine minerals (Na, Ca, Mg, K, Cu, Fe, Mn, Zn, and P) were determined with significant (p < 0.05) differences. The studied oils showed promising results and can be used in the food, cosmetics, and pharmaceutical industries. This is the first study on the eight L. siceraria seed varieties grown in Sudan, opening the way for further studies on these seeds.     

Quantification and Determination of Composition of Steryl Ferulates in Refined Rice Bran Oils Using an UPLC-MS Method

Gamma-oryzanol contains a mixture of steryl ferulates found in rice bran oil. Several studies have attributed nutraceutical properties to this mixture, such as hypocholesterolemic and anti-inflammatory activities. A method based on ultra-performance liquid chromatography coupled with electrospray ionization mass spectrometry was developed and evaluated for the simultaneous quantification of gamma-oryzanol and identification of five major steryl ferulates directly in refined rice bran oils (RBO) samples. The proposed method was evaluated according to linearity by obtaining standard curves with R ² values above 0.990, and limit of detection values ranged from 1.9 to 5.9 µg/mL, whereas limits of quantification ranged from 5.9 to 17.9 µg/mL; inter- and intraday accuracy and precision were within the range required by the US Food and Drug Administration guidelines; recovery levels ranged from 78 to 85% for gamma-oryzanol, and from 84 to 119% for steryl ferulates. The method can be considered robust in relation to the NH₄OH (ammonium hydroxide) content and cone voltage variations, with coefficient of variation and average relative percentage deviation values lower than 7.0 and 4.4%, respectively. The stability during the storage test was maintained in concentrated samples (18.5 µg/mL), with recovered values between 93 and 113%. This method was successfully applied to the analysis of RBO samples, demonstrating that it could be easily used for quality control purposes.     

Deterioration Kinetics of Crude Palm Oil,Canola Oil and Blend During Repeated Deep-Fat Frying

The oxidation of vegetable oils is generally treated as an apparent first order kinetic reaction. This study investigated the deterioration of crude palm oil (CPO), refined canola oil (RCO) and their blend (CPO:RCO 1:1 w/w) during 20 h of successive deep‐fat frying at 170, 180 and 190 °C. Kinetics of changes in oil quality indices, namely, free fatty acid (FFA), peroxide value (PV), anisidine value (p‐AV), total polar compounds (TPC) and color index (CI) were monitored. The results showed that FFA and PV accumulation followed the kinetic first order model, while p‐AV, TPC and CI followed the kinetic zero order model. The concentration and deterioration rate constants k, increased with increasing temperatures. This effect of temperature was modeled by the Arrhenius equation. The results showed that PV had the least activation energies E_a (kJ/mol) values of 5.4 ± 1 (RCO), 6.6 ± 0.7 (CPO) and 11.4 ± 1 (blend). The highest E_a requirement was exhibited by FFA with a range of 31.7 ± 3–76.5 ± 7 kJ/mol for the three oils. The overall E_a values showed that the stability of the blend was superior and not just intermediate of CPO and RCO. The correlation of the other oil quality indices with TPC indicated a positive linear correlation. The p‐AV displayed the strongest correlation, with mean correlation coefficient r_s of 0.998 ± 0.00, 0.994 ± 0.00 and 0.999 ± 0.00 for CPO, RCO and blend, respectively.     

Antioxidant Efficacy of a New Synergistic,Multicomponent Formulation for Fish Oil Omega-3 Concentrates

Today, tocopherols serve as the industrial standard antioxidant protection for fish oil omega-3 concentrates. Synergistic interactions between tocopherols, ascorbyl palmitate and natural polyphenols extracted from plant sources have been demonstrated in model systems. The main goal for this work was to develop a mix of such antioxidants with improved efficacy in the context of preserving industrial marine oil concentrates. The antioxidant formulation comprises tocopherols, ascorbyl palmitate, rosemary extract and green tea catechins. Part of the scope was to develop a method for dissolving green tea catechins in oil. The key element of the method is to introduce green tea on a lipid insoluble carrier when dissolving the extract in the oil, and thereafter remove the carrier by filtration. The antioxidant mix was tested against tocopherol in omega-3 concentrates of minimum 300 mg/g eicosapentaenoic acid (EPA) plus 200 mg/g docosahexaenoic acid (DHA) in the form of triacylglycerides and ethyl esters. The mix was superior compared to tocopherols in suppressing both primary- and secondary oxidation. Weight increase measurements of oil in contact with air correlated well with standard oxidation tests within individual samples and the method was considered simple and useful for monitoring oxidation in omega-3 concentrates.     

Comparison of Two Analytical Methods for Assessing Antioxidant Capacity of Rapeseed and Olive Oils

The oxygen radical absorbance capacity (ORAC) and the ferric reducing antioxidant power (FRAP) methods were used for the determination of antioxidant capacities (AC) of rapeseed oils at different steps of technological process and olive oils. The mean ORAC and FRAP results obtained for rapeseed oils (1,106–160 and 552–95.6 μmol TE/100 g) were higher than for olive oils (949–123 and 167–32.1 μmol TE/100 g). Although, FRAP values were lower than ORAC values for all studied oils, there is a linear and significant correlation between these two analytical methods (r = 0.9665 and 0.9298, P < 0.0005) for rapeseed and olive oils, respectively). Also, total phenolic compounds in rapeseed oils and olives correlated with antioxidant capacities (correlation coefficient ranged between 0.9470 and 0.8049). The refining process of rapeseed oils decreased the total phenolics content and antioxidant capacities by about 80%.     

有机相阴离子交换SPE-UPLC-UV法快速测定食用植物油中的抗氧化剂TBHQ和BHA

建立了基于有机相阴离子交换SPE前处理的UPLC-UV法,快速测定食用植物油中的抗氧化剂TBHQ和BHA。食用植物油样品用正己烷稀释后,直接上样至Oasis MAX聚合物材质阴离子交换SPE柱中进行净化,用正庚烷淋洗去除甘油酯成分,用0.5%甲酸-四氢呋喃溶液洗脱。以纯水和甲醇为流动相,TBHQ和BHA在Eclipse Plus C18上和梯度洗脱条件下3.4 min内达到基线分离;检测波长为290 nm;进样量为1μL。TBHQ和BHA在5~200 mg/L范围内线性关系良好(r≥0.999 95);在10、50、200 mg/kg这3个水平的加标回收率为91.5%~104%,相对标准偏差为1.2%~4.4%。方法定量限为0.5 mg/kg。与已有方法相比,该方法样品前处理更简便快速、色谱分离时间短、结果准确,可广泛用于食用植物油样品中TBHQ和BHA等抗氧化剂的快速检测。     

A Novel Method for Simultaneous Monitoring of 2-MCPD, 3-MCPD and Glycidyl Esters in Oils and Fats

The availability of a reliable methodology for the quantification of fatty acid esters of monochloropropropanediol (MCPD) and glycidol is essential for understanding the mechanism of formation of these process contaminants and for developing effective mitigation strategies. While several analytical methods for the determination of MCPD esters have already been developed and evaluated, only very few procedures are currently available for the analysis of glycidyl esters. This work presents a new indirect method for the simultaneous quantification of fatty acid esters of 2-MCPD, 3-MCPD and glycidol. The method is based on the acid-catalyzed conversion of glycidyl esters into 3-monobromopropanediol (3-MBPD) monoesters which, owing to the structural similarity to MCPD esters, are quantified by using the procedure we previously optimized for the analysis of MCPD esters. The critical step of the method, which is the conversion of glycidyl esters, was optimized by testing different reagent concentrations and varying other condition settings. The novel method showed good repeatability (RSD <2.5 %) and between-day reproducibility (RSD ≤5 %). The limit of detection was 0.04 mg/kg for bound 2-MCPD and 3-MCPD and 0.06 mg/kg for bound glycidol. The trueness of the method was evaluated by the analysis of spiked samples and by interlaboratory comparison.     

Comparison of Sample Preparation and Analysis Using Solid-Phase Extraction and Solid-Phase Microextraction to Determine Monohydroxy PAH in Urine by GC/HRMS

Sample preparation techniques using solid-phase extraction (SPE) and solid-phase microextraction (SPME) are compared for the analysis of monohydroxy polycyclic aromatic hydrocarbons (OHPAH) in human urine. Urine samples spiked with five carbon-13 labeled internal standards are first enzymatically hydrolyzed. Sixteen OHPAH from eight parent compounds (naphthalene, fluorene, phenanthrene, fluoranthene, pyrene, chrysene, benzo[ c ]phenanthrene, and benz[ a ]anthracene) are then extracted along with the internal standards by these two different techniques. The analytes are derivatized by a silylating reagent before final analysis. Final separation and detection are performed by temperature-programmed capillary gas chromatography (GC) and high-resolution mass spectrometry (HRMS). The two extraction techniques are compared for sample preparation time, cost, throughput, reinjection possibility, frequency of outliers, matrix interference, signal linearity, and method detection limit. SPE demonstrates major advantages over SPME for most of these aspects.     

理工教融合的《仪器分析》课程教学团队建设探索

以湖南科技学院生化系仪器分析课程师资队伍建设为例,提出了建设理工教融合的《仪器分析》课程教学团队的思路,为地方新建本科院校《仪器分析》课程教学团队建设提供了参考与示范。     

中国特色水溶液全循环法尿素工艺节能降耗技术剖析

采用我国自行开发的尿素合成塔塔板和等温型内件、预分离-预蒸馏工艺流程,形成了具有中国特色的水溶液全循环法尿素工艺。分析了采用新型尿素合成塔塔板和等温内件对提高尿素合成塔转化率、降低一段分解加热器汽耗的作用,介绍了中压段多回收反应热能的Q-1100工艺以及水溶液全循环工艺装置中进一步降低汽耗的潜力。     

Theoretical and Kinetic Tools for Selecting Effective Antioxidants: Application to the Protection of Omega-3 Oils with Natural and Synthetic Phenols

Radical-scavenging antioxidants play crucial roles in the protection of unsaturated oils against autoxidation and, especially, edible oils rich in omega-3 because of their high sensitivity to oxygen. Two complementary tools are employed to select, among a large set of natural and synthetic phenols, the most promising antioxidants. On the one hand, density functional theory (DFT) calculations provide bond dissociation enthalpies (BDEs) of 70 natural (i.e., tocopherols, hydroxybenzoic and cinnamic acids, flavonoids, stilbenes, lignans, and coumarins) and synthetic (i.e., 2,6-di-tert-butyl-4-methylphenol (BHT), 3-tert-butyl-4-hydroxyanisol (BHA), and tert-butylhydroquinone (TBHQ)) phenols. These BDEs are discussed on the basis of structure–activity relationships with regard to their potential antioxidant activities. On the other hand, the kinetic rate constants and number of hydrogen atoms released per phenol molecule are measured by monitoring the reaction of phenols with 2,2-diphenyl-1-picrylhydrazyl (DPPH^•) radical. The comparison of the results obtained with these two complementary methods allows highlighting the most promising antioxidants. Finally, the antioxidant effectiveness of the best candidates is assessed by following the absorption of oxygen by methyl esters of linseed oil containing 0.5 mmol L⁻¹ of antioxidant and warmed at 90 °C under oxygen atmosphere. Under these conditions, some natural phenols namely epigallocatechin gallate, myricetin, rosmarinic and carnosic acids were found to be more effective antioxidants than α-tocopherol.     

An overall assessment of a new adhesive bonding process for composite materials,with regard to quality and cost

An assessment of innovative adhesive bonding process has been performed with regard to quality and cost. In this frame, the effect of two different atmospheric pressure plasma surface treatment conditions on the fracture toughness behaviour of adhesively bonded joints was experimentally investigated. Furthermore, the mechanical performance of a newly developed aerospace structural adhesive has been characterised experimentally in order to assess the quality of the bonded elements. To assess the feasibility of the new process, a complete cost-estimation analysis of the process has been carried out based on the activity-based costing modelling approach, thus serving to the estimation of the total cost/duration of the process. To this end, the newly developed process is assessed with regard to quality and cost. It could be shown that the new process offers tempting alternatives to the existing adhesive bonding and joining processes used in the aeronautic industry.     

Variation of discharge capacities with C-rate for LiNi1−yMyO2 (M = Ni,Ga, Al and/or Ti) cathodes synthesized by the combustion method

LiNiO₂, LiNi_0.995Al_0.005O₂, LiNi_0.975Ga_0.025O₂, LiNi_0.990Ti_0.010O₂ and LiNi_0.990Al_0.005Ti_0.005O₂ specimens were synthesized by preheating at 400 °C for 30 min in air and calcination at 750 °C for 36 h in an O₂ stream. The variation of the discharge capacities with C-rate for the synthesized samples was investigated. LiNi_0.990Al_0.005Ti_0.005O₂ has the largest first discharge capacities at the 0.1 and 0.2 C rates. LiNi_0.990Ti_0.010O₂ has the largest first discharge capacity at the 0.5 C rate. In case of LiNiO₂ and LiNi_0.990Ti_0.010O₂, the first discharge capacity decreases slowly as the C-rate increases. LiNiO₂ has the largest discharge capacities at n = 10 (after stabilization of the cycling performance) at the 0.1, 0.2 and 0.5 C rates. This is considered to be related with the largest value of I_0 0 3/I_1 0 4 and the smallest value of R-factor (the least degree of cation mixing) among all the samples. LiNi_0.975Ga_0.025O₂ exhibits the lowest discharge capacity degradation rates at 0.1, 0.2 and 0.5 C rates.