Estimating Octanol–Water Partition Coefficients of Novel Brominated Flame Retardants by Reversed-Phase High-Performance Liquid Chromatography and Computational Models

IF 3.6 4区环境科学与生态学 Q2 ENVIRONMENTAL SCIENCES Environmental Toxicology and Chemistry Pub Date : 2024-07-23 DOI:10.1002/etc.5952

Anthony J. Sigman-Lowery, Dominic M. Di Toro, Yu-Ping Chin

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Abstract

Legacy brominated flame retardants, including polybrominated diphenyl ethers (PBDEs), have been classified as persistent organic pollutants and replaced with novel brominated flame retardants (NBFRs). The octanol–water partition coefficients (log K_OW) of NBFRs have been computationally estimated, but the log K_OW values provided by these methods can differ by 1 to 3 orders of magnitude. Given the importance of this parameter in fate and toxicity models, we indirectly measured the log K_OW values of eight NBFRs by their capacity factor (k′) on a reversed-phase high-performance liquid chromatography (HPLC) C18 column by isocratic elution and compared these measured values with those estimated by nine computational models. Log K_OW values were obtained for the NBFRs 1,2-bis(2,4,6-tribromophenoxy) ethane, pentabromobenzene, pentabromoethylbenzene, pentabromotoluene, 2-ethylhexyl 2,3,4,5-tetrabromobenzoate, allyl 2,4,6-tribromophenylether, 2,3-dibromopropyl-2,4,6-tribromophenyl ether, and bis(2-ethylhexyl) tetrabromophthalate. A training set of phthalates, polychlorinated biphenyls, PBDEs, and halogenated benzenes were chosen to obtain the log k′–log K_OW calibration for the NBFRs. The computational models KowWIN, XLogP3, EAS-E Suite, COSMOtherm, DirectML, and Abraham polyparameter linear free energy relationships all predicted the log K_OW values of the calibration compounds to within 1 order of magnitude without significant bias. The median of these models predicted log K_OW values for the calibration compounds that were close to those known in the literature with root mean square error (RMSE) = 0.224 and for the NBFRs that were close to those measured by HPLC (RMSE = 0.334). Environ Toxicol Chem 2024;43:2105–2114. © 2024 SETAC

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利用反相高效液相色谱法和计算模型估算新型溴化阻燃剂的辛醇-水分配系数

包括多溴联苯醚 (PBDE) 在内的传统溴化阻燃剂已被列为持久性有机污染物，并被新型溴化阻燃剂 (NBFR) 所取代。NBFR 的辛醇-水分配系数（log KOW）已经过计算估算，但这些方法提供的对数 KOW 值可能相差 1 到 3 个数量级。鉴于该参数在归宿和毒性模型中的重要性，我们在反相高效液相色谱（HPLC）C18 柱上通过等度洗脱法，用容量因子（k'）间接测量了八种 NBFR 的对数 KOW 值，并将这些测量值与九种计算模型估算的值进行了比较。得出了 1,2-双（2,4,6-三溴苯氧基）乙烷、五溴苯、五溴乙苯、五溴甲苯、2-乙基己基 2、3,4,5-四溴苯甲酸 2-乙基己酯、2,4,6-三溴苯烯丙基醚、2,3-二溴丙基-2,4,6-三溴苯醚和双(2-乙基己基)四溴邻苯二甲酸酯。选择了一组邻苯二甲酸盐、多氯联苯、多溴联苯醚和卤代苯的训练集，以获得 NBFR 的对数 k'-log KOW 校准。计算模型 KowWIN、XLogP3、EAS-E Suite、COSMOtherm、DirectML 和亚伯拉罕多参数线性自由能关系对校准化合物的对数 KOW 值的预测均在 1 个数量级以内，没有明显偏差。这些模型的中位数预测出的校准化合物的对数 KOW 值接近文献中已知的 KOW 值（均方根误差 (RMSE) = 0.224），预测出的 NBFR 值接近 HPLC 测得的 KOW 值（均方根误差 (RMSE) = 0.334）。环境毒物化学 2024;00:1-10。© 2024 SETAC.

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来源期刊

Environmental Toxicology and Chemistry 环境科学-毒理学

CiteScore

7.40

自引率

9.80%

发文量

265

审稿时长

3.4 months

期刊介绍： The Society of Environmental Toxicology and Chemistry (SETAC) publishes two journals: Environmental Toxicology and Chemistry (ET&C) and Integrated Environmental Assessment and Management (IEAM). Environmental Toxicology and Chemistry is dedicated to furthering scientific knowledge and disseminating information on environmental toxicology and chemistry, including the application of these sciences to risk assessment.[...] Environmental Toxicology and Chemistry is interdisciplinary in scope and integrates the fields of environmental toxicology; environmental, analytical, and molecular chemistry; ecology; physiology; biochemistry; microbiology; genetics; genomics; environmental engineering; chemical, environmental, and biological modeling; epidemiology; and earth sciences. ET&C seeks to publish papers describing original experimental or theoretical work that significantly advances understanding in the area of environmental toxicology, environmental chemistry and hazard/risk assessment. Emphasis is given to papers that enhance capabilities for the prediction, measurement, and assessment of the fate and effects of chemicals in the environment, rather than simply providing additional data. The scientific impact of papers is judged in terms of the breadth and depth of the findings and the expected influence on existing or future scientific practice. Methodological papers must make clear not only how the work differs from existing practice, but the significance of these differences to the field. Site-based research or monitoring must have regional or global implications beyond the particular site, such as evaluating processes, mechanisms, or theory under a natural environmental setting.

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