Residual weakly bound ligands influence biological compatibility of mixed ligand shell, thiol-stabilized gold nanoparticles,Environmental Science: Nano

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Residual weakly bound ligands influence biological compatibility of mixed ligand shell, thiol-stabilized gold nanoparticles
Environmental Science: Nano ( IF 5.8 ) Pub Date : 2017-06-28 00:00:00 , DOI: 10.1039/c7en00363c
Lisa Truong _{1,

2,

3,

4} , Tatiana Zaikova _{4,

5,

6,

7} , Nicole M. Schaeublin _{8,

9,

10,

11,

12} , Ki-Tae Kim _{13,

14,

15,

16} , Saber M. Hussain _{8,

9,

10,

11,

12} , James E. Hutchison _{4,

5,

6,

7} , Robert L. Tanguay _{1,

2,

3,

4}

Affiliation

Department of Environmental and Molecular Toxicology
Oregon State University
Corvallis
USA
Department of Chemistry and Biochemistry
University of Oregon
Eugene
Molecular Bioeffects Branch
Bioeffects Division
Airman System Directorate
711th Human Performance Wing
Air Force Research Laboratory
Department of Environmental Engineering
Seoul National University of Science & Technology
Seoul 01811
South Korea

Mixed ligand shells are frequently employed to impart multiple and new functions to inorganic nanoparticles. Mixtures of ligands also result from incomplete or partial ligand exchange reactions wherein one that is more tightly bound replaces a weakly bound ligand. Little is known about how the ligand compositions in mixed shell nanoparticles influence biological activity. Further, the impact of residual weakly bound ligands is not understood. To examine the biological impacts due to weakly bound ligands within a mixed ligand shell, a series of six types of gold nanoparticles (AuNPs) were synthesized that have the same core size and possess ligand shells that are predominately either 2-mercaptoethanesulfonate (MES) or N,N,N-trimethylammoniumethanethiol (TMAT), but contain varying (small) amounts of residual triphenylphosphine (TPP). Each member of the series was carefully examined to determine the core size (by small-angle X-ray scattering and transmission electron microscopy) and ligand shell composition (by ¹H NMR spectroscopy and X-ray photoelectron spectroscopy). The influence of the residual, weakly bound TPP ligands upon the biological activity of the nanoparticles (NPs) was evaluated in zebrafish embryos and subsequently in human keratinocyte cells. In the embryos, the presence of residual TPP led to increased cell death that is linked to increased oxidative stress. Control experiments suggest that these effects are not the result of free ligand. Exposure of the keratinocyte cells to the TMAT-containing nanoparticles demonstrated similar results in that residual TPP decreased cell viability, likely through increased ROS generation. The results of these studies suggest that the use of strongly bound ligands that passivate the surface of the inorganic core can prevent ROS and, therefore, yield nanoparticles with reduced biological effects.

中文翻译：

残留的弱结合配体影响混合配体壳，硫醇稳定的金纳米颗粒的生物相容性

混合配体壳经常用于赋予无机纳米颗粒多种和新的功能。配体的混合物也来自不完全或部分配体交换反应，其中更紧密结合的取代了弱结合的配体。关于混合壳纳米粒子中的配体组成如何影响生物活性，人们所知甚少。此外，尚不了解残留的弱结合配体的影响。为了检查由于混合配体壳内弱结合的配体引起的生物影响，合成了一系列六种类型的金纳米颗粒（AuNP），它们具有相同的核心尺寸，并具有主要为2-巯基乙磺酸盐（MES）或配体壳的配体壳N，N，N-三甲基乙硫醇铵（TMAT），但含有变化（少量）的残留三苯膦（TPP）。仔细检查了该系列的每个成员，以确定核的大小（通过小角度X射线散射和透射电子显微镜）和配体壳组成（通过¹1 H NMR光谱和X射线光电子能谱）。在斑马鱼胚胎中，然后在人角质形成细胞中，评估了残留的弱结合TPP配体对纳米粒子（NP）生物学活性的影响。在胚胎中，残留TPP的存在导致细胞死亡增加，而细胞死亡与氧化应激增加有关。对照实验表明，这些作用不是游离配体的结果。角质形成细胞暴露于含TMAT的纳米颗粒也显示出相似的结果，即残留的TPP降低了细胞活力，这可能是由于ROS生成增加所致。这些研究的结果表明，使用钝化无机核表面的强结合配体可以防止ROS，因此可产生生物效应降低的纳米颗粒。

更新日期：2017-08-10

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