Polymers as Reference Partitioning Phase: Polymer Calibration for an Analytically Operational Approach To Quantify Multimedia Phase Partitioning
Polymers as Reference Partitioning Phase: Polymer Calibration for an Analytically Operational Approach To Quantify Multimedia Phase Partitioning
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DOI：
10.1021/acs.analchem.6b00393
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发表时间：
2016-06-07
影响因子：
7.4
通讯作者：
Mayer, Philipp
中科院分区：
文献类型：
--
作者：
Gilbert, Dorothea;Witt, Gesine;Mayer, Philipp
在许多基于分析分配的测量技术中，聚合物越来越多地用于从各种类型的样品和介质中富集疏水有机化学品（HOC）。我们建议使用聚合物作为参考分配相，并引入聚合物-聚合物分配作为基础，更深入地了解聚合物之间HOCs的分配差异，校准分析方法，以及现有分配系数的一致性检查和新分配系数的计算。通过在甲醇-水溶液中平衡13种有机硅，包括聚二甲基硅氧烷（PDMS）和低密度聚乙烯（LDPE），测定了多氯联苯（PCB）、多环芳烃（PAH）和有机氯农药（OCPs）的聚合物-聚合物分配系数。甲醇作为助溶剂可确保所有聚合物达到平衡，而其对聚合物性能的影响并不显著影响有机硅-有机硅分配系数。然而，我们注意到轻微的共溶剂对确定的聚合物-聚合物分配系数的影响。聚合物-聚合物分配系数接近1，证实了几种PDMS材料具有相同的吸收能力，而有机硅组内以及有机硅与LDPE之间存在较大的偏离。由于不精确的涂层厚度或填料的存在，聚合物体积的不确定性被确定为分配系数的误差来源。通过应用聚合物作为参考分配相的新概念并使用聚合物-聚合物分配系数作为转换因子，计算了新的基于聚合物的（LDPE-脂质、PDMS-空气）和多介质分配系数（脂质-水、空气-水）。本研究鼓励使用的聚合物-聚合物分配系数，认识到聚合物可以作为一个连接的第三阶段的定量了解的平衡分配的HOCs之间的任何两个阶段。
Polymers are increasingly applied for the enrichment of hydrophobic organic chemicals (HOCs) from various types of samples and media in many analytical partitioning-based measuring techniques. We propose using polymers as a reference partitioning phase and introduce polymer polymer partitioning as the basis for a deeper insight into partitioning differences of HOCs between polymers, calibrating analytical methods, and consistency checking of existing and calculation of new partition coefficients. Polymer-polymer partition coefficients were determined for polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), and organochlorine pesticides (OCPs) by equilibrating 13 silicones, including polydimethylsiloxane (PDMS) and low-density polyethylene (LDPE) in methanol-water solutions. Methanol as cosolvent ensured that all polymers reached equilibrium while its effect on the polymers' properties did not significantly affect silicone-silicone partition coefficients. However, we noticed minor cosolvent effects on determined polymer-polymer partition coefficients. Polymer-polymer partition coefficients near unity confirmed identical absorption capacities of several PDMS materials, whereas larger deviations from unity were indicated within the group of silicones and between silicones and LDPE. Uncertainty in polymer volume due to imprecise coating thickness or the presence of fillers was identified as the source of error for partition coefficients. New polymer-based (LDPE-lipid, PDMS-air) and multimedia partition coefficients (lipid-water, air-water) were calculated by applying the new concept of a polymer as reference partitioning phase and by using polymer-polymer partition coefficients as conversion factors. The present study encourages the use of polymer-polymer partition coefficients, recognizing that polymers can serve as a linking third phase for a quantitative understanding of equilibrium partitioning of HOCs between any two phases.