Panczyk Tomasz, Wolski Pawel, Nieszporek Krzysztof
Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences ul, Niezapominajek 8, Cracow 30239, Poland.
Department of Theoretical Chemistry, Institute of Chemical Sciences, Faculty of Chemistry, Maria Curie-Sklodowska University in Lublin pl., Maria Curie-Sklodowska 3, Lublin 20031, Poland.
J Phys Chem B. 2025 May 8;129(18):4581-4594. doi: 10.1021/acs.jpcb.5c01362. Epub 2025 Apr 28.
This study examines the interaction between degraded polyethylene terephthalate (PET) nanoparticles and human serum albumin (HSA), focusing on the effects of nanoparticle size and surface modifications resulting from degradation. PET degradation, induced via shock compression in water, leads to significant chemical alterations, including the formation of hydroxyl, carboxyl, and carbonyl groups. These modifications influence the hydrophilicity of PET nanoparticles and their binding behavior with HSA. The production of degraded PET nanoparticles involves subjecting pristine PET to controlled shock compression in an aqueous environment, which initiates chemical reactions similar to those that may occur during degradation. The degradation process is characterized by a progressive breakdown of polymer chains, leading to an increase in functionalized surface groups that enhanced hydrophilicity. The performed analysis of surface chemistry reveals that the introduction of oxygen-containing groups alters the interaction properties of PET nanoparticles, making them more prone to hydrogen bonding with water molecules while simultaneously reducing their affinity for HSA binding. Molecular dynamics simulations, umbrella sampling, and weighted histogram analysis are employed to investigate the thermodynamic aspects of PET-HSA interactions. The study identifies preferred binding sites of PET nanoparticles on HSA, revealing that degraded PET nanoparticles preferentially bind to Domain I and Domain III of HSA. Interaction energy analysis demonstrates that larger PET nanoparticles exhibit stronger binding, whereas small degraded nanoparticles have significantly reduced interaction energies, indicating a higher likelihood of desorption. Further structural analysis using root-mean-squared deviation (RMSD) and root-mean-squared fluctuation (RMSF) confirms that PET binding does not significantly alter HSA's secondary structure. However, degradation significantly increases PET hydrophilicity, weakening their adsorption onto HSA. Large PET nanoparticles are strongly bound, whereas small degraded nanoparticles remain unbound, raising concerns regarding their potential toxicity due to free migration in the bloodstream. These findings provide crucial insights into the biological implications of PET degradation, the role of surface chemistry in determining nanoparticle interactions, and their potential contributions to nanoplastic toxicity.
本研究考察了降解聚对苯二甲酸乙二酯（PET）纳米颗粒与人血清白蛋白（HSA）之间的相互作用，重点关注纳米颗粒尺寸以及降解导致的表面修饰的影响。通过在水中进行冲击压缩诱导的PET降解会导致显著的化学变化，包括羟基、羧基和羰基的形成。这些修饰影响PET纳米颗粒的亲水性及其与HSA的结合行为。降解PET纳米颗粒的制备过程包括在水环境中对原始PET进行可控的冲击压缩，这引发了类似于降解过程中可能发生的化学反应。降解过程的特征是聚合物链逐渐断裂，导致功能化表面基团增加，从而增强了亲水性。表面化学分析表明，含氧基团的引入改变了PET纳米颗粒的相互作用特性，使其更容易与水分子形成氢键，同时降低了它们与HSA结合的亲和力。采用分子动力学模拟、伞形采样和加权直方图分析来研究PET - HSA相互作用的热力学方面。该研究确定了PET纳米颗粒在HSA上的优先结合位点，表明降解的PET纳米颗粒优先结合到HSA的结构域I和结构域III。相互作用能分析表明，较大的PET纳米颗粒表现出更强的结合力，而小的降解纳米颗粒的相互作用能显著降低，表明解吸的可能性更高。使用均方根偏差（RMSD）和均方根波动（RMSF）进行的进一步结构分析证实，PET的结合不会显著改变HSA的二级结构。然而，降解显著增加了PET的亲水性，削弱了它们在HSA上的吸附。大的PET纳米颗粒紧密结合，而小的降解纳米颗粒未结合，这引发了对它们在血液中自由迁移可能产生的潜在毒性的担忧。这些发现为PET降解的生物学影响、表面化学在确定纳米颗粒相互作用中的作用以及它们对纳米塑料毒性的潜在贡献提供了关键见解。
