A Comparison of the Migration of ‘Spiked’ and ‘Intrinsic’ Substances from Paper and Board into Raisins and into Tenax as a Food Simulant

Four samples of paper and board (P/B) of a type used for packaging dry foods were subjected to migration experiments using raisins and the polymeric powder Tenax as a food simulant. The P/B samples contained only low levels of diisopropylnaphthalene (DiPN) and diisobutyl phthalate (DiBP), and so, experiments were also conducted after spiking the P/B with added model substances. These were o‐xylene, acetophenone, dodecane, benzophenone, DiPN and DiBP. Migration experiments into raisins and Tenax were conducted for 10 days at 40°C. Migration levels depended strongly on the nature of the substance. Migration from spiked P/B samples was more extensive (as a percentage of that available) than migration of intrinsic migratable substances, and so, studying spiked samples tends to be conservative. It is considered likely that this is because of binding of substances, especially aromatics with pi‐electrons such as DiPN and DiBP, to active sites on the surface of P/B fibres, resulting in non‐linear absorption isotherms. However, further work would be needed to prove this conclusively. Considering the results overall and also that raisins packed in P/B can have a shelf life of up to 1 year at ambient temperatures, the test results using Tenax as a food simulant are considered to be appropriate without application of a correction factor. Copyright © 2014 John Wiley & Sons, Ltd.     

Do phosphoric acid esters affect the immediate enamel bond strengths?

Purpose: To investigate the effects of phosphoric acid esters (PAEs)-containing primers on the micro-tensile bond strengths (MTBS) of etched enamel, the micro-morphologies of the resin–enamel interfaces, and the enamel surfaces.

Materials and Methods: Thirty-three bovine incisors were used in this study. After the labial enamel surfaces were highly polished, they were etched, water sprayed, and air-dried. Afterward, the enamel surfaces were treated with or without (control) one of three PAEs-containing primers (40%MDP, Ivoclar Vivadent; Resulcin AquaPrime A + B, DMG; Xeno V, Dentsply), water sprayed, and air-dried. Subsequently, an adhesive Heliobond (Ivoclar Vivadent) was applied and resin composite (Core Build-up, Bisco) was placed incrementally. They were prepared into multiple beams of about 1 × 1 × 8 mm for MTBS tests. The enamel surfaces and resin–enamel interfaces were analyzed by SEM and TEM. The data were analyzed by two-way ANOVA and LSD test.

Results: Using PAEs-containing primers could increase the enamel MTBS (p < 0.05). The primer MDP produced higher MTBS than the primer Resulcin AquaPrime A + B and Xeno V. The SEM findings revealed the primed enamel surfaces were covered with a thin or glue-like layer of monomer-calcium salts of PAEs and the residual enamel crystallites, and various micro-porosities were detected within the hybrid layers. The TEM findings revealed the hydroxyapatite crystallites were tightly covered by the adhesive, the adhesive mixed with resin composite, or sparse irregular enamel crystallites.

Conclusion: The application of PAEs-containing primers on the etched enamel substrate could significantly increase the immediate enamel bond strengths. However, this effect was dependent on the individual PAEs-containing primer used.     

Production and Emulsifying Effect of Polyglycerol and Fatty Acid Esters with Varying Degrees of Esterification

Esters with acyl groups can be formed by the esterification of polyglycerol. The purpose of the present study was to produce fatty acid esters [hexanoic (caproic), octanoic (caprylic), decanoic (capric), dodecanoic (lauric), tetradecanoic (myristic), hexadecanoic (palmitic), octadecanoic (stearic)] and polyglycerol (average number‐of degrees of polymerization of 5) with varying degrees of esterification and to examine their emulsifying properties. A number of fundamental catalysts of polyglycerol acylation reactions by methyl esters of carboxylic acid were studied, and sodium methoxide was found to be the best choice. The temperature rate of transesterification increased from 180 to 220 °C with the fatty acid chain alkyl residue. Synthesized mono‐, di‐, tri‐, tetra‐, and heptaesters of various fatty acids and polyglycerol provided the highest hydroxyl values from 15 to 815 mg KOH g^?1 and saponification values from 82 to 321 mg KOH g^?1. The emulsifying properties were assessed for all polyglycerol and fatty acid esters, with results showing maximum emulsifying effect for tri‐ and tetraesters of capric, lauric, and caprylic acids. Regardless of the hydrophilic–lipophilic balance value (HLB) of polyglycerol esters and carboxylic acid, a 4:1 ratio of sunflower oil to water formed a water‐in‐oil type emulsion. When mixing oil and water in a 1:1 ratio, mono‐ and diesters of polyglycerol formed an oil‐in‐water type emulsion, heptaesters formed a water‐in‐oil type emulsion, and tri‐ and tetraesters formed both of types of emulsions, depending on the length of the acid hydrocarbon radicals.     

Solubilization Behavior of Phorbol Esters from Jatropha Oil in Surfactant Micellar Solutions

Phorbol esters (PEs) are important toxic compounds found in Jatropha curcas oil and pressed seeds. These compounds are tumor promoters; thus, their removal prior to further utilization of the pressed seed is important. This work aimed to investigate the solubilization behavior of PEs and Jatropha oil in nonionic [effect of the ethylene oxide number (EON), carbon‐chain length and temperature] and anionic (NaCl addition) surfactant systems. The results reveal that an increase in the EON of the nonionic surfactant molecules, rather than an increase in the carbon‐chain length, enhances PE solubilization. The hydrophile‐lipophile balance (HLB) value was correlated with PE solubilization for nonionic surfactant solutions. The solubilization of PEs decreased slightly with increasing temperature, in contrast to solubilization of the oil. Moreover, the mole fraction of PE solubilized in the micelle decreased with increasing electrolyte concentration in anionic surfactant solutions. The solubilization behavior of PEs in both nonionic and anionic solutions indicates that PE acts more like a polar compound than a nonpolar compound. In addition, the PEs in nonionic micelles are likely located in the palisade region (i.e., between the head group and the first few carbon atoms of the tail), whereas those in anionic micelles are likely near the outer core of the head group. This finding suggests that a nonionic surfactant with a higher EON has a greater potential to extract PE from Jatropha seeds. If an anionic surfactant is combined as co‐surfactant, a small amount of electrolyte should be added to increase PE solubilization.     

超高效合相色谱-串联质谱法测定口含烟中对羟基苯甲酸酯

建立了QuEChERS-超高效合相色谱-串联质谱法（UPC²-MS/MS）测定口含烟中对羟基苯甲酸酯类防腐剂。采用乙腈提取,基质分散固相萃取净化,UPC^{2 TM} HSS C18 SB色谱柱（3.0 mm×100 mm×1.8 μm）分离,内标法定量。优化后的对羟基苯甲酸酯的合相色谱分离条件为：主要流动相为CO₂,改性剂为甲醇-异丙醇混合溶液（V/V,1∶1）,系统流速1.5 mL/min,离子化辅助溶剂（补偿溶剂）为0.1%甲酸-甲醇溶液,动态备压1.03×10⁷ Pa,柱温55 ℃,可在3 min内完成单个样品分析。4种成分的线性范围均为0.5~5.0 mg/kg;在低、中、高加标水平下,方法的平均回收率为94.6%~105.6%,相对标准偏差小于5%。实际样品测定结果表明,单个成分的含量和多种成分的总含量均小于10 mg/kg,低于GB 2760-2014对于此类防腐剂在食品中添加限量的要求。该方法环境友好、高效、准确,适用于口含烟中对羟基苯甲酸酯类物质的测定。     

固相萃取技术在增塑剂测定中的应用

增塑剂污染严重凸显对其监测的必要性,痕量邻苯二甲酸酯增塑剂需要在测试前进行富集预处理。固相萃取技术是一种净化和富集相结合的新型样品预处理技术,也是目前在环境样品测试中使用最广泛的预处理新技术。本文结合其在邻苯二甲酸酯类化合物分析中的应用对该技术的原理、固定相类型、效率影响因素和柱性能考察作了介绍。     

Solvent-Assisted Crystallization of Fatty Acid Alkyl Esters from Animal Fat

An easy and efficient method for the separation of saturated and unsaturated fatty acid mono alkyl esters, prepared from animal fat, was developed. The most efficient separation was achieved by the use of solvents such as methanol and acetone at low temperatures. The dilution of the alkyl esters with 10 times the amount of solvent (10:1 v/w) and storage of the mixture for 4 h at ?22 °C could be defined as optimum conditions. After filtration of the saturated fraction at the corresponding temperature very pure fractions were obtained. For fatty acid methyl esters deriving from tallow, with an initial content of saturated fatty acids of almost 50 %, a saturated ester fraction with only 5 % unsaturated fatty acids and an unsaturated ester fraction with about 9 % of saturated fatty acids could be obtained. The solvent easily could be recovered by distillation. In addition fatty acid ethyl, 1‐propyl, 2‐propyl, 1‐butyl, tert‐butyl and 3‐methyl‐1‐butyl esters were prepared and separated into saturated and unsaturated fractions. All fractions were analyzed according to the fatty acid compositions and showed similar or slightly worse results compared to the methyl esters. The cold filter plugging points of the unsaturated fractions were measured, showing the lowest value for the unsaturated methyl ester fraction at ?26 °C. The fractionation with the use of solvents is an easy tool in order to obtain fatty acid alkyl esters with excellent cold temperature behavior out of animal fat.     

The Optimization of the Production of Methyl Esters from Corn Oil Using Barium Hydroxide as a Heterogeneous Catalyst

In recent years, vegetable oils, as renewable raw materials, became a promising feedstock for chemicals and biodiesel production. The main products derived from oils are esters of fatty acids, especially methyl esters, obtained by their transesterification with methanol, in presence of acid or alkaline catalysts. The use of such catalysts implies the need for washing operations, which leads to environmental pollution. In the present paper, the response surface methodology based on a central composite design, has been developed to optimize the process of transesterification of corn oil. Ba(OH)₂ in presence of diethyl ether was used as catalyst. A quadratic polynomial equation was obtained. It correlates the reaction parameters [methanol/oil molar ratio (x _r), reaction time (x _t) and catalyst concentration (x _c)] with methyl esters yield. Analysis of variance analysis showed that only methanol/oil molar ratio and catalyst concentration have had the most significant influences on the conversion. The maximum methyl esters yield was obtained using the following optimum parameters: methanol/corn oil ratio of 11.32, reaction time of 118 min and catalyst concentration of 3.6 wt%.     

Hybrid dual-curable cyanate ester/boron phosphate composites via sequential thiol-ene photopolymerization and thermal polymerization

The aim of this study was to improve hybrid dual-curable cyanate ester/boron phosphate composites via sequential thiol-ene photopolymerization and thermal polymerization for high performance applications such as aerospace and electronic devices. A novel 2,2′-diallylbisphenol A dicyanate ester (DA-BADCy) which is the allyl group containing cyanate ester was synthesized and characterized. DA-BADCy, silicon containing monofunctional thiol compound, trifunctional thiol compound and boron phosphate were cured using both ultraviolet (UV) and thermal methods. Using thiol-ene system, cyanate ester formulations, which are normally prepared at high temperatures, were prepared at room temperature. This study maintains ease of application for cyanate esters. Thermal stability, flammability and thermal conductivity of the samples were evaluated by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), limiting oxygen index (LOI) and laser flash method, respectively. The samples were characterized with the following analysis; gel content, water absorption capacity and stress–strain test. Hydrophobicity of the samples was determined by the contact angle measurements. Moreover, the surface morphology of the samples was investigated by a scanning electron microscopy (SEM–EDS). The obtained results prove that the composites have good thermal and mechanical properties and with the help of easier preparation techniques, they can be used in many applications such as aerospace, electronic devices, materials engineering.