Sánchez-Paz Verónica, Pastoriza-Gallego Maria José, Losada-Barreiro Sonia, Bravo-Díaz Carlos, Gunaseelan K, Romsted Laurence S
Facultad de Ciencias, Departamento de Química Física, Universidad de Vigo, 36200 Vigo, Spain.
J Colloid Interface Sci. 2008 Apr 1;320(1):1-8. doi: 10.1016/j.jcis.2007.12.018. Epub 2007 Dec 23.
Until recently, determining the distribution of antioxidants, AOs, between the oil, interfacial and aqueous regions of opaque emulsions has not worked well because the concentrations of AOs in interfacial regions cannot be determined separately from their concentrations in the oil and water phases. However, our novel kinetic method based on the reaction between an arenediazonium ion and vitamin E, or alpha-tocopherol, provides the first good estimates for the two partition constants that describe alpha-tocopherol distribution between the oil/interfacial and water/interfacial regions of tributyrin/Brij 30/water emulsions without physical isolation of any phase. The reaction is monitored by a new derivatization method based on trapping unreacted arenediazonium ion as an azo dye and confirmed by linear sweep voltammetry, LSV. The results by both derivatization and LSV methods are in good agreement and show that alpha-tocopherol distributes strongly in favor of the interfacial region when the oil is tributyrin, e.g., ca. 90% when the surfactant volume fraction is Phi I=0.01. The second-order rate constant for reaction in the interfacial region is also obtained from the results. Our kinetic method provides a robust approach for determining antioxidant distributions in emulsions and should help develop a quantitative interpretation of antioxidant efficiency in emulsions.
直到最近,确定不透明乳液的油相、界面相和水相区域中抗氧化剂(AO)的分布情况一直不太顺利,因为无法将界面区域中AO的浓度与其在油相和水相中的浓度分开测定。然而,我们基于芳基重氮离子与维生素E(即α-生育酚)之间反应的新型动力学方法,首次对两个分配常数给出了较好的估计值,这两个常数描述了α-生育酚在三丁酸甘油酯/Brij 30/水乳液的油/界面和水/界面区域之间的分布情况,且无需对任何相进行物理分离。该反应通过一种新的衍生化方法进行监测,该方法基于将未反应的芳基重氮离子捕获为偶氮染料,并通过线性扫描伏安法(LSV)进行确认。衍生化方法和LSV方法得到的结果吻合良好,结果表明,当油相为三丁酸甘油酯时,α-生育酚强烈分布于界面区域,例如,当表面活性剂体积分数为Phi I = 0.01时,约90%的α-生育酚分布于界面区域。还从结果中获得了界面区域反应的二级速率常数。我们的动力学方法为确定乳液中抗氧化剂的分布提供了一种可靠的方法,应该有助于对乳液中抗氧化剂效率进行定量解释。