Palma Susana I C J, Marciello Marzia, Carvalho Alexandra, Veintemillas-Verdaguer Sabino, Morales Maria Del Puerto, Roque Ana C A
REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal.
Departamento de Biomateriales y Materiales Bioinspirados, Instituto de Ciencia de Materiales de Madrid, ICMM/CSIC, 28049 Madrid, Spain.
J Colloid Interface Sci. 2015 Jan 1;437:147-155. doi: 10.1016/j.jcis.2014.09.019. Epub 2014 Sep 18.
Oleic acid coated iron oxide nanoparticles synthesized by thermal decomposition in organic medium are highly monodisperse but at the same time are unsuitable for biological applications. Ligand-exchange reactions are useful to make their surface hydrophilic. However, these could alter some structural and magnetic properties of the modified particles. Here we present a comprehensive study and comparison of the effects of employing either citric acid (CA) or meso-2,3-dimercaptosuccinic acid (DMSA) ligand-exchange protocols for phase transfer of monodisperse hydrophobic iron oxide nanoparticles produced by thermal decomposition of Fe(acac)3 in benzyl ether. We show the excellent hydrodynamic size distribution and colloidal stability of the hydrophilic particles obtained by the two protocols and confirm that there is a certain degree of oxidation caused by the ligand-exchange. CA revealed to be more aggressive towards the iron oxide surface than DMSA and greatly reduced the saturation magnetization values and initial susceptibility of the resulting particles compared to the native ones. Besides being milder and more straightforward to perform, the DMSA ligand exchange protocol produces MNP chemically more versatile for further functionalization possibilities. This versatility is shown through the covalent linkage of gum Arabic onto MNP-DMSA using carboxyl and thiol based chemical routes and yielding particles with comparable properties.
通过在有机介质中热分解合成的油酸包覆氧化铁纳米颗粒具有高度单分散性,但同时不适用于生物应用。配体交换反应有助于使其表面具有亲水性。然而,这些反应可能会改变改性颗粒的一些结构和磁性。在此,我们对采用柠檬酸(CA)或中-2,3-二巯基琥珀酸(DMSA)配体交换方案对通过在苄醚中热分解Fe(acac)3制备的单分散疏水性氧化铁纳米颗粒进行相转移的效果进行了全面研究和比较。我们展示了通过这两种方案获得的亲水性颗粒具有出色的流体动力学尺寸分布和胶体稳定性,并证实配体交换会导致一定程度的氧化。结果表明,与DMSA相比,CA对氧化铁表面的侵蚀性更强,与原始颗粒相比,所得颗粒的饱和磁化强度值和初始磁化率大大降低。除了更温和且操作更直接外,DMSA配体交换方案还使磁性纳米颗粒在化学上更具通用性,便于进一步进行功能化。通过使用基于羧基和硫醇的化学路线将阿拉伯胶共价连接到MNP-DMSA上并得到具有可比性质的颗粒,展示了这种通用性。