Kampferbeck Michael, Vossmeyer Tobias, Weller Horst
Institute of Physical Chemistry , University of Hamburg , Grindelallee 117 , 20146 Hamburg , Germany.
Langmuir. 2019 Jul 2;35(26):8790-8798. doi: 10.1021/acs.langmuir.9b01060. Epub 2019 Jun 19.
Most applications of nanoparticles require robust stabilization, for example, by surface-bound ligands or the encapsulation within polymer shells. Furthermore, for biomedical applications, the particles must be dispersible in a complex biological environment. Thus, high-quality nanoparticles synthesized in organic solvents must be transferred into aqueous media. Here, we present a novel scalable method enabling the robust hydrophilic encapsulation of non-agglomerated nanoparticles by growing polystyrene shells via AGET-ATRP in microemulsion. To demonstrate this approach, we encapsulate iron oxide nanoparticles (diameter: 13.7 ± 0.6 nm). Because the ATRP initiator is grafted onto the nanoparticles' surface, the shells are covalently attached to the iron oxide cores. By varying the amount of monomers, the shell thickness can be adjusted precisely, as indicated by the increasing hydrodynamic size from ∼22 to 26 nm (DLS, number mean) with an increasing amount of added monomers. Moreover, the degree of cross-linking can be controlled by the amount of added divinylbenzene (DVB). To evaluate the robustness of the polymer shells against ion infusion, we introduce a novel colorimetric method, which is based on the formation of the red iron thiocyanate complex. After addition of HCl, the increase in absorbance at 468 nm indicates leaching of iron ions from the polymer-encapsulated core particles. These measurements confirm that with increasing shell thickness, significantly improved shielding is achieved. Furthermore, high concentrations of added DVB [33-50% (v/v) in a monomer mixture] improve the shielding effect. However, when smaller amounts of DVB were added [10-25% (v/v)], the shielding effect was diminished, even in comparison to non-cross-linked polymer shells. This finding suggests a higher porosity of shells with a low degree of cross-linking.
纳米颗粒的大多数应用都需要强大的稳定性,例如通过表面结合的配体或封装在聚合物壳层内来实现。此外,对于生物医学应用,颗粒必须能够在复杂的生物环境中分散。因此,在有机溶剂中合成的高质量纳米颗粒必须转移到水性介质中。在此,我们提出了一种新颖的可扩展方法,通过在微乳液中经由ARGET-ATRP生长聚苯乙烯壳层,实现对非团聚纳米颗粒的强大亲水性封装。为了证明这种方法,我们封装了氧化铁纳米颗粒(直径:13.7±0.6纳米)。由于ATRP引发剂接枝到纳米颗粒表面,壳层与氧化铁核共价连接。通过改变单体的量,可以精确调整壳层厚度,如动态光散射(DLS,数均)显示,随着添加单体量的增加,流体力学尺寸从约22纳米增加到26纳米。此外,交联度可以通过添加二乙烯基苯(DVB)的量来控制。为了评估聚合物壳层对离子注入的稳定性,我们引入了一种基于红色硫氰酸铁络合物形成的新型比色法。加入HCl后,468纳米处吸光度的增加表明铁离子从聚合物封装的核心颗粒中浸出。这些测量结果证实,随着壳层厚度的增加,屏蔽效果显著提高。此外,高浓度添加的DVB[在单体混合物中为33 - 50%(v/v)]可改善屏蔽效果。然而,当添加较少量的DVB[10 - 25%(v/v)]时,即使与非交联聚合物壳层相比,屏蔽效果也会减弱。这一发现表明交联度低的壳层具有更高的孔隙率。
J Colloid Interface Sci. 2015-1-5
Nanomaterials (Basel). 2021-9-21
Soft Matter. 2005-6-27
Top Curr Chem (Cham). 2020-5-7