Kotchey Gregg P, Gaugler James A, Kapralov Alexander A, Kagan Valerian E, Star Alexander
Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania, USA.
J Mater Chem B. 2013;1(3):302-309. doi: 10.1039/C2TB00047D.
The growing applications of carbon nanotubes (CNTs) inevitably increase the risk of exposure to this potentially toxic nanomaterial. In an attempt to address this issue, research has been implemented to study the biodegradation of CNTs. In particular, myeloperoxidase (MPO), an enzyme expressed by inflammatory cells of animals including humans, catalyse the degradation of oxidized carbon nanomaterials. While reactive intermediates generated by MPO efficiently degrade oxidized single-walled carbon nanotubes (o-SWCNTs); the exact mechanism of enzyme-catalysed biodegradation remains ambiguous. In this work, we tried to explain enzymatic oxidation in terms of redox potentials by employing competitive substrates for MPO such as chloride, which is oxidized by MPO to form a strong oxidant (hypochlorite), and antioxidants that have lower redox potentials than CNTs. Employing transmission electron microscopy, Raman spectroscopy, and vis-NIR absorption spectroscopy, we demonstrate that the addition of antioxidants, L-ascorbic acid and L-glutathione, with or without chloride significantly mitigates MPO-catalysed biodegradation of o-SWCNTs. This study focuses on a fundamental understanding of the mechanisms of enzymatic biodegradation of CNTs and the impact of antioxidants on these pathways.
碳纳米管(CNTs)应用的不断增加不可避免地提高了接触这种潜在有毒纳米材料的风险。为了解决这个问题,人们开展了研究以探讨碳纳米管的生物降解情况。具体而言,髓过氧化物酶(MPO)是包括人类在内的动物炎症细胞所表达的一种酶,它能催化氧化态碳纳米材料的降解。虽然MPO产生的反应性中间体能够有效降解氧化态单壁碳纳米管(o-SWCNTs),但其酶促生物降解的确切机制仍不明确。在这项工作中,我们试图通过使用MPO的竞争性底物(如被MPO氧化形成强氧化剂(次氯酸盐)的氯离子)以及氧化还原电位低于碳纳米管的抗氧化剂,从氧化还原电位的角度来解释酶促氧化过程。利用透射电子显微镜、拉曼光谱和可见-近红外吸收光谱,我们证明添加抗氧化剂L-抗坏血酸和L-谷胱甘肽,无论有无氯离子,都能显著减轻MPO催化的o-SWCNTs生物降解。本研究着重于对碳纳米管酶促生物降解机制以及抗氧化剂对这些途径影响的基本理解。