利用单颗粒 ICP-MS 测定/表征人尿液中的二氧化钛和银纳米粒子的可能性。

Possibilities of single particle-ICP-MS for determining/characterizing titanium dioxide and silver nanoparticles in human urine.

机构信息

Trace Element, Spectroscopy and Speciation Group (GETEE), Strategic Grouping in Materials (AEMAT), Department of Analytical Chemistry, Nutrition and Bromatology, Faculty of Chemistry. Universidade de Santiago de Compostela, Avenida das Ciencias, s/n. 15782, Santiago de Compostela, Spain; Faculty of Pharmacy, General and Toxicological Chemistry Department, Azerbaijan Medical University, Bakihanov Street, 23. AZ1022, Baku, Azerbaijan.

出版信息

J Trace Elem Med Biol. 2019 Jul;54:55-61. doi: 10.1016/j.jtemb.2019.04.003. Epub 2019 Apr 9.

DOI:10.1016/j.jtemb.2019.04.003

PMID:31109621

Abstract

OBJECTIVE

The current use of nanoparticles in personal care and cosmetics, food safety, agriculture, medicine and pharmacy has led to a growing concern on the toxicity of these emerging materials to humans and also to the environment. Nanoparticles assessment (determination and size distribution) is a challenge mainly due to limitations of the current analytical instrumentation, but also because nanoparticles in foodstuff and environmental samples are usually found at low concentrations. The scenario is even more critical when dealing with clinical samples, mainly when trying to assess nanoparticles at basal levels in complex samples such as blood and urine. The aim of this paper is to find data regarding the presence of nanoparticles at basal levels in urine human samples.

METHODS

The use of single particle - inductively couple plasma - mass spectrometry (sp-ICP-MS) has been explored to determine and characterize silver and titanium dioxide nanoparticles in human urine. Urine samples were directly diluted (1:5 to 1:10) with 1%(v/v) glycerol before sp-ICP-MS measurements, and efforts were made for validating the over-all procedure.

RESULTS

The limit of detection and quantification for Ag NPs were 5.72 × 10 and 1.91 × 10 Ag NPs mL, respectively; whereas, values for TiO NP concentrations were 4.31 × 10 and 1.44 × 10 TiO NPs mL. The limit of detection in size after applying several methods (3σ/5σ criteria) was found to be within the 8-9 nm for Ag NPs, and from 15 to 18 nm for TiO NPs. Within-batch precision for Ag NP concentration was 15% (11% for mean size of nanoparticle distributions). Repeatability for TiO NPs was 25% (TiO NP concentration) and 9% (TiO NP mean size). Good analytical recovery rates were found for spiked experiments with Ag NP standards of 40 and 60 nm (values within the 104-106% range), and also for TiO NPs of 50 and 100 nm (96-98%). Finally, basal levels of Ag NPs and TiO NPs, as well as total Ag and Ti concentrations, in human urine were assessed. Low Ag and Ag NP concentrations were found. Ag NPs exhibited mean sizes of approximately 16-17 nm. Total Ti levels, however, were higher than total Ag concentration, and TiO NP concentrations within the 1.56 × 10-2.80 × 10 NPs mL range were measured (TiO NP mean sizes were from 76 to 98 nm).

摘要

目的

目前纳米粒子在个人护理和化妆品、食品安全、农业、医药和制药领域的应用，引发了人们对这些新兴材料对人类和环境毒性的日益关注。纳米粒子评估（测定和粒径分布）是一个挑战，主要是由于当前分析仪器的局限性，但也因为食品和环境样品中的纳米粒子通常浓度较低。当处理临床样本时，情况甚至更加关键，特别是在尝试评估血液和尿液等复杂样本中的基础水平纳米粒子时。本文旨在寻找关于人尿液中基础水平纳米粒子存在的数据。

方法

本文采用单颗粒-电感耦合等离子体质谱（sp-ICP-MS）来测定和表征人尿中的银和二氧化钛纳米粒子。尿液样品直接用 1%（v/v）甘油稀释（1:5 至 1:10），然后对整个过程进行了验证。

结果

Ag NPs 的检出限和定量限分别为 5.72×10 和 1.91×10 Ag NPs mL；而 TiO NP 浓度的检出限分别为 4.31×10 和 1.44×10 TiO NPs mL。经过几种方法（3σ/5σ 标准）应用后，Ag NPs 的粒径检测限发现为 8-9nm，而 TiO NPs 的粒径检测限为 15-18nm。Ag NP 浓度的批内精密度为 15%（纳米粒子分布的平均粒径为 11%）。TiO NP 的重复性为 25%（TiO NP 浓度）和 9%（TiO NP 平均粒径）。Ag NP 标准 40nm 和 60nm 的加标实验以及 TiO NP 标准 50nm 和 100nm 的加标实验均得到了良好的分析回收率（回收率在 104-106%范围内）。最后，评估了人尿液中 Ag NPs 和 TiO NPs 的基础水平以及总 Ag 和 Ti 浓度。发现 Ag 和 Ag NP 浓度较低。Ag NPs 的平均粒径约为 16-17nm。然而，总 Ti 水平高于总 Ag 浓度，并且测量到 1.56×10-2.80×10 NPs mL 范围内的 TiO NP 浓度（TiO NP 的平均粒径为 76-98nm）。