Dutz Silvio, Buske Norbert, Landers Joachim, Gräfe Christine, Wende Heiko, Clement Joachim H
Institute of Biomedical Engineering and Informatics (BMTI), Technische Universität Ilmenau, D-98693 Ilmenau, Germany.
Department of Nano Biophotonics, Leibniz Institute of Photonic Technology (IPHT), D-07745 Jena, Germany.
Nanomaterials (Basel). 2020 May 27;10(6):1019. doi: 10.3390/nano10061019.
Magnetite (FeO) particles with a diameter around 10 nm have a very low coercivity (H) and relative remnant magnetization (M/M), which is unfavorable for magnetic fluid hyperthermia. In contrast, cobalt ferrite (CoFeO) particles of the same size have a very high H and M/M, which is magnetically too hard to obtain suitable specific heating power (SHP) in hyperthermia. For the optimization of the magnetic properties, the Fe ions of magnetite were substituted by Co step by step, which results in a Co doped iron oxide inverse spinel with an adjustable Fe substitution degree in the full range of pure iron oxide up to pure cobalt ferrite. The obtained magnetic nanoparticles were characterized regarding their structural and magnetic properties as well as their cell toxicity. The pure iron oxide particles showed an average size of 8 nm, which increased up to 12 nm for the cobalt ferrite. For ferrofluids containing the prepared particles, only a limited dependence of H and M/M on the Co content in the particles was found, which confirms a stable dispersion of the particles within the ferrofluid. For dry particles, a strong correlation between the Co content and the resulting H and M/M was detected. For small substitution degrees, only a slight increase in H was found for the increasing Co content, whereas for a substitution of more than 10% of the Fe atoms by Co, a strong linear increase in H and M/M was obtained. Mössbauer spectroscopy revealed predominantly Fe in all samples, while also verifying an ordered magnetic structure with a low to moderate surface spin canting. Relative spectral areas of Mössbauer subspectra indicated a mainly random distribution of Co ions rather than the more pronounced octahedral site-preference of bulk CoFeO. Cell vitality studies confirmed no increased toxicity of the Co-doped iron oxide nanoparticles compared to the pure iron oxide ones. Magnetic heating performance was confirmed to be a function of coercivity as well. The here presented non-toxic magnetic nanoparticle system enables the tuning of the magnetic properties of the particles without a remarkable change in particles size. The found heating performance is suitable for magnetic hyperthermia application.
直径约10纳米的磁铁矿(FeO)颗粒具有非常低的矫顽力(H)和相对剩余磁化强度(M/M),这对于磁流体热疗是不利的。相比之下,相同尺寸的钴铁氧体(CoFeO)颗粒具有非常高的H和M/M,其磁性太强以至于在热疗中难以获得合适的比热功率(SHP)。为了优化磁性能,磁铁矿中的铁离子被钴逐步取代,这导致了一种钴掺杂的氧化铁反尖晶石,其铁取代度在从纯氧化铁到纯钴铁氧体的整个范围内均可调节。对所获得的磁性纳米颗粒的结构和磁性能以及细胞毒性进行了表征。纯氧化铁颗粒的平均尺寸为8纳米,而钴铁氧体的平均尺寸增加到了12纳米。对于含有制备颗粒的铁磁流体,仅发现H和M/M对颗粒中钴含量的依赖性有限,这证实了颗粒在铁磁流体中的稳定分散。对于干燥颗粒,检测到钴含量与所得的H和M/M之间存在很强的相关性。对于较小的取代度,随着钴含量的增加,仅发现H略有增加,而当超过10%的铁原子被钴取代时,H和M/M获得了强烈的线性增加。穆斯堡尔光谱显示所有样品中主要为铁,同时也证实了具有低至中等表面自旋倾斜的有序磁结构。穆斯堡尔子谱的相对谱面积表明钴离子主要呈随机分布,而不是块状CoFeO中更明显的八面体位置偏好。细胞活力研究证实,与纯氧化铁纳米颗粒相比,钴掺杂的氧化铁纳米颗粒的毒性没有增加。磁加热性能也被证实是矫顽力的函数。这里展示的无毒磁性纳米颗粒系统能够在不显著改变颗粒尺寸的情况下调节颗粒的磁性能。所发现的加热性能适用于磁热疗应用。
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