金纳米粒子悬浮液的离子特异性稳定性

Philipp Ritzert, Alexandra Striegel, Regine von Klitzing
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摘要

金纳米粒子(AuNPs)因其广泛的应用和生物相容性而在基础研究和开发中发挥着重要作用。本研究探讨了三种 AuNP 悬浮液在加入著名的霍夫迈斯特系列钠盐(NaF、NaCl、NaBr、NaI、NaSCN)(盐浓度介于 10 mM 和 100 mM 之间)后的老化情况。这些 AuNP 类型在尺寸(直径 5 nm 与 11 nm)和封端类型(物理吸附的柠檬酸盐与共价结合的巯基丙酸 (MPA))上有所不同。我们通过光学(吸收光谱、摄影)和电子显微镜监测 AuNPs 的聚集情况和悬浮液的稳定性。盐浓度的较大变化会导致胶体稳定性的巨大差异,例如,从稳定的悬浮液到沉淀后的快速失稳。尤其是各向同性盐 NaI 和 NaSCN 以截然不同的方式强烈改变了吸收光谱。NaI 将 AuNP 聚合在一起,影响了主吸收,而 NaSCN 在聚合过程中保持 AuNP 结构的能力比其他卤化钠要强得多,从而产生了次吸收峰。虽然减小 AuNPs 的尺寸会导致更稳定的悬浮液,但由于总可用表面的增加,离子特异性效应更加明显。即使是共价结合的 MPA 覆层也无法稳定 AuNPs 使其免受 NaI 的粒子融合,尽管它能延缓这一过程。尽管离子对胶体分散体稳定性的不同影响之间存在着复杂的相互作用,但本研究还是将不同的影响从静电屏蔽(通过界面吸附和 AuNPs 的桥接)到离子与 AuNPs 的封端剂之间的竞争进行了区分。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Ion-specific Stability of Gold Nanoparticle Suspensions
Gold nanoparticles (AuNPs) play an important role in fundamental research and development due to their versatile applications and biocompatibility. This study addresses the aging of three AuNP suspensions after the addition of various sodium salts along the well-known Hofmeister series (NaF, NaCl, NaBr, NaI, NaSCN) at different salt concentrations between 10 mM and 100 mM. The AuNP types differ in size (5 nm vs. 11 nm in diameter) and the capping type (physisorbed citrate vs. covalently bound mercaptopropionic acid (MPA)). We monitor the aggregation of the AuNPs and the suspension stability optically (absorption spectroscopy, photography) and by electron microscopy. The large range of salt concentrations results in a large variety of colloidal stability, e.g., from stable suspensions to fast destabilization followed by sedimentation. At intermediate and high salt concentration strong ion-specific effects emerge that are non-monotonous with respect to the Hofmeister series. In particular, the chaotropic salts, NaI and NaSCN, strongly alter the absorption spectra in very different ways. NaI fuses AuNPs together influencing the primary absorption, while NaSCN retains AuNP structure during aggregation much stronger than the remaining sodium halides, resulting in a secondary absorption peak. Although decreasing the size of AuNPs leads to more stable suspensions, the ion specific effects are even more pronounced due to the increase in total available surface. Even the covalently bound MPA capping is not able to stabilize AuNPs against particle fusion by NaI, although it delays the process. Despite the complex interplay between different effects of ions on the stability of colloidal dispersions, this study disentangles the different effects from electrostatic screening, via adsorption at the interface and bridging of AuNPs, to the competition between ions and the capping agent of the AuNPs.
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