Centro Integrativo de Quimica y Biologia Aplicada (CIBQA), Universidad Bernardo O'Higgins, Santiago, Chile.
CICECO-Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal.
Phys Chem Chem Phys. 2021 Feb 25;23(7):4133-4140. doi: 10.1039/d0cp06086k.
Although aqueous biphasic systems have been largely investigated in the separation and/or purification of biocompounds, their potential as reaction media to design integrated reaction-separation processes has been less explored. In this work aqueous biphasic systems (ABSs) composed of polypropylene glycol of molecular weight 400 g mol-1 (PPG 400) and different polyethylene glycols (PEGs) were characterized, and investigated for integrated reaction-separation processes, i.e. in the nucleophilic degradation of diazinon and further separation of reaction products by taking advantage of the lower-critical solution temperature (LCST) behaviour of these ABSs. The nucleophilic degradation of diazinon was carried out in the monophasic regime at 298 K, after which an increase in temperature (up to 313 K) allowed the product separation by two-phase formation (thermoreversible systems). The reaction kinetics and reaction pathways have been determined. The reaction kinetic increases as the PEG molecular weight decreases, with the half-life values obtained being competitive to those previously reported using volatile organic solvents as solvent media and significantly higher than under alkaline hydrolysis. One reaction pathway occurs in ABSs comprising PEGs of higher molecular weights, whereas in the ABS composed of PEG 600 two reaction pathways have been identified, meaning that the reaction pathways can be tailored by changing the PEG nature. ABSs formed by PEGs of lower molecular weights were identified as the most promising option to separate the pesticide degradation products by simply applying changes in temperature.
尽管双水相系统在生物化合物的分离和/或纯化方面已经得到了广泛的研究,但它们作为反应介质来设计集成反应-分离过程的潜力尚未得到充分探索。在这项工作中,我们对由分子量为 400 克/摩尔的聚丙二醇(PPG 400)和不同的聚乙二醇(PEG)组成的双水相系统(ABS)进行了表征,并研究了它们在集成反应-分离过程中的应用,即在敌百虫的亲核降解以及利用这些 ABS 的低临界溶解温度(LCST)行为进一步分离反应产物。在 298 K 下,在单相区进行敌百虫的亲核降解,然后升高温度(高达 313 K),通过两相形成(热可逆系统)实现产物分离。确定了反应动力学和反应途径。反应动力学随 PEG 分子量的降低而增加,获得的半衰期值与以前使用挥发性有机溶剂作为溶剂介质报道的值相当,并且明显高于碱性水解条件下的值。在由高分子量 PEG 组成的 ABS 中发生一种反应途径,而在由 PEG 600 组成的 ABS 中则鉴定出两种反应途径,这意味着可以通过改变 PEG 的性质来调整反应途径。由低分子量 PEG 形成的 ABS 被鉴定为通过简单地改变温度来分离农药降解产物的最有前途的选择。