Department of Chemistry, York University, Toronto, Ontario M3J 1P3, Canada.
Analyst. 2021 Sep 13;146(18):5756-5766. doi: 10.1039/d1an01089a.
People spend up to 90% of their time indoors, and yet our understanding of indoor air quality and the chemical processes driving it are poorly understood, despite levels of key pollutants typically being higher indoors compared to outdoors. Nitrous acid (HONO) is a species that drives these indoor chemical processes, with potentially detrimental health effects. In this work, a BODIPY-based probe was synthesized with the aim of developing the first selective passive sampler for atmospheric HONO. Our probe and its products are easily detected by UV-Vis spectroscopy with molar extinct coefficients of 37 863 and 33 787 M cm, respectively, and a detection limit of 14.8 ng mL. When protonated, the probe fluoresces with a quantum yield of 33%, which is turned off upon reaction. The synthesized BODIPY probe was characterized using NMR and UV-Vis spectroscopy. Products were characterized by UV-Vis and ultra high-resolution mass spectrometry. The reaction kinetics of the probe with nitrite was studied using UV-Vis spectroscopy, which had a pseudo-first-order rate of = 7.7 × 10 s. The rapid reaction makes this probe suitable for targeted ambient sampling of HONO. This was investigated through a proof-of-concept experiment with gaseous HONO produced by a custom high-purity calibration source delivering the sample to the BODIPY probe in an acidic aqueous solution in clean air and a real indoor air matrix. The probe showed quantitative uptake of HONO in both cases to form the same products observed from reaction with nitrite, with no indication of interferences from ambient NO or NO. The chemical and physical characteristics of the probe therefore make it ideal for use in passive samplers for selective sampling of HONO from the atmosphere.
人们在室内的时间长达 90%,但我们对室内空气质量和推动空气质量变化的化学过程的理解还很有限,尽管关键污染物的浓度通常比室外高。亚硝酸(HONO)是一种驱动室内化学过程的物质,可能对健康有不利影响。在这项工作中,合成了一种基于 BODIPY 的探针,旨在开发用于大气 HONO 的首个选择性被动采样器。我们的探针及其产物很容易通过紫外-可见光谱检测到,摩尔消光系数分别为 37863 和 33787 M cm,检测限为 14.8 ng mL。质子化后,探针的荧光量子产率为 33%,反应后荧光猝灭。使用 NMR 和紫外-可见光谱对合成的 BODIPY 探针进行了表征。通过紫外-可见光谱和超高效分辨率质谱对产物进行了表征。使用紫外-可见光谱研究了探针与亚硝酸盐的反应动力学,其伪一级速率常数 = 7.7 × 10 s。快速反应使该探针适用于目标环境中 HONO 的采样。这通过一个概念验证实验进行了研究,该实验使用定制的高纯校准源产生的气态 HONO,将样品输送到酸性水溶液中的 BODIPY 探针中,在清洁空气中和真实的室内空气基质中进行采样。探针在这两种情况下都显示出对 HONO 的定量吸收,形成与与亚硝酸盐反应相同的产物,没有表明来自环境 NO 或 NO 的干扰。因此,探针的化学和物理特性使其成为从大气中选择性采样 HONO 的被动采样器的理想选择。