College of Environmental Science and Engineering, State Key Laboratory of Pollution Control and Resource Reuse, Tongji University , Shanghai 200092, China.
School of Radiation Medicine and Protection & School for Radiological and Interdisciplinary Sciences (RAD-X), Medical College of Soochow University , Suzhou, Jiangsu 215123, China.
ACS Nano. 2017 Jan 24;11(1):501-515. doi: 10.1021/acsnano.6b06495. Epub 2017 Jan 3.
The safe implementation of nanotechnology requires nanomaterial hazard assessment in accordance with the material physicochemical properties that trigger the injury response at the nano/bio interface. Since CuO nanoparticles (NPs) are widely used industrially and their dissolution properties play a major role in hazard potential, we hypothesized that tighter bonding of Cu to Fe by particle doping could constitute a safer-by-design approach through decreased dissolution. Accordingly, we designed a combinatorial library in which CuO was doped with 1-10% Fe in a flame spray pyrolysis reactor. The morphology and structural properties were determined by XRD, BET, Raman spectroscopy, HRTEM, EFTEM, and EELS, which demonstrated a significant reduction in the apical Cu-O bond length while simultaneously increasing the planar bond length (Jahn-Teller distortion). Hazard screening was performed in tissue culture cell lines and zebrafish embryos to discern the change in the hazardous effects of doped vs nondoped particles. This demonstrated that with increased levels of doping there was a progressive decrease in cytotoxicity in BEAS-2B and THP-1 cells, as well as an incremental decrease in the rate of hatching interference in zebrafish embryos. The dissolution profiles were determined and the surface reactions taking place in Holtfreter's solution were validated using cyclic voltammetry measurements to demonstrate that the Cu/Cu and Fe/Fe redox species play a major role in the dissolution process of pure and Fe-doped CuO. Altogether, a safe-by-design strategy was implemented for the toxic CuO particles via Fe doping and has been demonstrated for their safe use in the environment.
为了确保纳米技术的安全应用，需要根据纳米材料在纳米/生物界面引发损伤反应的物理化学特性来评估纳米材料的危害。由于氧化铜纳米颗粒（NPs）在工业上被广泛应用，并且其溶解性能对危害潜力起着重要作用，因此我们假设通过颗粒掺杂使 Cu 与 Fe 更紧密地结合，可以通过减少溶解来构成一种更安全的设计方法。因此，我们在火焰喷雾热解法反应器中设计了一个组合文库，其中 CuO 掺杂了 1-10%的 Fe。通过 XRD、BET、拉曼光谱、HRTEM、EFTEM 和 EELS 确定了形貌和结构特性，结果表明，在同时增加平面键长（Jahn-Teller 畸变）的情况下，顶角 Cu-O 键长显著缩短。在组织培养细胞系和斑马鱼胚胎中进行了危害筛选，以区分掺杂和未掺杂颗粒的危害效应变化。这表明，随着掺杂水平的增加，BEAS-2B 和 THP-1 细胞的细胞毒性逐渐降低，斑马鱼胚胎孵化干扰的速度也逐渐降低。还确定了溶解曲线，并使用循环伏安法测量来验证 Holtfreter 溶液中发生的表面反应，以证明 Cu/Cu 和 Fe/Fe 氧化还原物种在纯和 Fe 掺杂 CuO 的溶解过程中起着重要作用。总之，通过 Fe 掺杂实现了对有毒 CuO 颗粒的安全设计策略，并已证明其在环境中安全使用。
