Gorb Leonid, Sosnowska Anita, Bulawska Natalia, Leszczynska Danuta, Puzyn Tomasz, Leszczynski Jerzy
Institute of Molecular Biology and Genetics, NAS of Ukraine, 150 Zabolotny Str.,, Kiev, 03143, Ukraine.
Laboratory of Environmental Chemoinformatics, Department of Environmental Chemistry and Radiochemistry, Faculty of Chemistry, University of Gdansk, Gdansk, Poland.
J Mol Model. 2025 Sep 13;31(10):269. doi: 10.1007/s00894-025-06491-9.
Perfluoroalkyl and polyfluoroalkyl substances (PFAS), with over 15,000 types listed in the US EPA's CompTox database, are found in everyday items like textiles, packaging, firefighting foams, and medical devices. Their widespread use has led to concerning health effects-including cancers, elevated cholesterol, and fertility issues-with detectable levels present in 98% of Americans. While perfluorooctanoic (PFOA) and perfluorooctanesulphonic (PFOS) are among the most studied, their environmental behavior and ecological interactions remain poorly understood. Advances in computer-based methods, including chemoinformatics and quantum modeling, now aid in predicting properties and simulating PFAS dynamics. Biochar (BC), produced via biomass pyrolysis under limited oxygen, is known for its porosity and adsorption capabilities. Magnetic biochar (MBC), enhanced with iron-based compounds, adds the benefit of magnetic separation, making it ideal for water decontamination. This paper explores the use of MBC to remove PFOA and PFOS from the environment, leveraging computational tools to investigate molecular interactions and adsorption properties.
A doubled crystallographic unit of hematite (Fe₂₄O₃₆) was constructed and fully optimized using density functional theory (DFT) with the M06-2X functional. Geometry optimization used the 6-31G(d,p) basis set, while single-point energies were calculated with 6-311 + + G(d,p). Antiferromagnetic conditions were ensured by setting the total spin to zero (Sz = 0), and triplet instability analysis was performed to evaluate ferromagnetic potential. To simulate bulk water effects on adsorption, the CPCM solvation model (ε = 78.3) was applied. Harmonic frequency analysis confirmed structural minima, and Gibbs free energies were calculated using Gaussian 16. PFOA and PFOS, with highly negative pKa values (~ -0.1 and <). Quadratic SCF convergence (scf = qc) addressed numerical challenges, and interaction energies were corrected for basis set superposition error using the counterpoise method. Calculated IR spectra and molecular visualizations were generated with Chemcraft, without applying scaling factors.
全氟烷基和多氟烷基物质（PFAS）在美国环境保护局（EPA）的综合毒性数据库中列出的种类超过15000种，存在于纺织品、包装、消防泡沫和医疗设备等日常用品中。它们的广泛使用已导致令人担忧的健康影响，包括癌症、胆固醇升高和生育问题，98%的美国人身体中都存在可检测到的PFAS水平。虽然全氟辛酸（PFOA）和全氟辛烷磺酸（PFOS）是研究最多的两种物质，但它们的环境行为和生态相互作用仍知之甚少。基于计算机的方法，包括化学信息学和量子建模的进展，现在有助于预测PFAS的性质并模拟其动态过程。通过生物质在有限氧气下热解产生的生物炭（BC），以其孔隙率和吸附能力而闻名。用铁基化合物增强的磁性生物炭（MBC）增加了磁分离的优势，使其成为水净化的理想选择。本文探讨了利用MBC从环境中去除PFOA和PFOS的方法，利用计算工具研究分子相互作用和吸附特性。
构建了赤铁矿（Fe₂₄O₃₆）的双晶胞单元，并使用密度泛函理论（DFT）和M06-2X泛函进行了完全优化。几何优化使用6-31G(d,p)基组，单点能量用6-311++G(d,p)计算。通过将总自旋设置为零（Sz = 0）确保反铁磁条件，并进行三重态不稳定性分析以评估铁磁势。为了模拟大量水对吸附的影响，应用了CPCM溶剂化模型（ε = = 78.3）。谐波频率分析确认了结构最小值，并使用高斯16计算了吉布斯自由能。PFOA和PFOS的pKa值非常负（约为-0.1和<）。二次SCF收敛（scf = qc）解决了数值挑战，并使用平衡法对基组叠加误差校正了相互作用能。计算得到的红外光谱和分子可视化图是用Chemcraft生成的，未应用比例因子。
