Laboratorio de Materiales para Análisis Químico (MAT4LL), Departamento de Química, Unidad Departamental de Química Analítica, Universidad de La Laguna (ULL), Tenerife, 38206, Spain; Laboratory for Process Engineering, Environment, Biotechnology and Energy (LEPABE), Department of Chemical Engineering, University of Porto, Porto, 4200-465, Portugal.
Laboratorio de Materiales para Análisis Químico (MAT4LL), Departamento de Química, Unidad Departamental de Química Analítica, Universidad de La Laguna (ULL), Tenerife, 38206, Spain.
Talanta. 2021 Sep 1;232:122440. doi: 10.1016/j.talanta.2021.122440. Epub 2021 Apr 23.
A headspace solid-phase microextraction (HS-SPME) method was developed using the metal-organic framework (MOF) CIM-80(Al) as extraction phase and in combination with gas chromatography-mass spectrometry (GC-MS) for the simultaneous determination of 6 methylsiloxanes and 7 musk fragrances in different environmental waters. The chromatographic separation was optimized in different GC instruments equipped with different detectors, allowing the correct separation and identification of the compounds. The HS-SPME method was optimized using a Box-Behnken experimental design, while the validation was carried out together with the most suitable commercial fiber (divinylbenzene/polydimethylsiloxane) for comparison purposes. The MOF-based coating was particularly efficient for the determination of volatile methylsiloxanes, showing moderately lower limits of detection (of 0.2 and 0.5 μg Lversus 0.6 μg L for cyclic methylsiloxanes) and slightly better precision (relative standard deviation values lower than 17% versus 22%) than the commercial coating, while avoiding the cross-contamination issues associated to the polymeric composition of commercial fibers. The method was applied for the analysis of seawater and wastewater samples, allowing the quantification of several analytes and the assessment of matrix effects. The proposed HS-SPME method using the CIM-80(Al) fiber constitutes a more environmentally friendly, simpler, and efficient strategy in comparison with other sample preparation methods using different extraction techniques, while the use of a MOF as fiber sorbent constitutes a potential alternative to exploit the features of SPME for the challenging environmental monitoring of these compounds.
采用金属-有机骨架（MOF）CIM-80（Al）作为萃取相，结合气相色谱-质谱联用（GC-MS），建立了同时测定不同环境水样中 6 种甲基硅氧烷和 7 种麝香香精的顶空固相微萃取（HS-SPME）方法。在不同配备不同检测器的 GC 仪器上优化了色谱分离条件，使化合物得到正确分离和鉴定。采用 Box-Behnken 实验设计对 HS-SPME 方法进行了优化，同时与最适合的商业纤维（二乙烯基苯/聚二甲基硅氧烷）一起进行了验证，以作比较。基于 MOF 的涂层对挥发性甲基硅氧烷的测定特别有效，其检测限（环状甲基硅氧烷为 0.2 和 0.5μg/L，而商业纤维为 0.6μg/L）略低，精密度略高（相对标准偏差值低于 17%，而商业纤维为 22%），同时避免了商用纤维聚合组成带来的交叉污染问题。该方法应用于海水和废水样品的分析，可定量分析多种分析物，并评估基质效应。与使用不同萃取技术的其他样品制备方法相比，采用 CIM-80（Al）纤维的 HS-SPME 方法更环保、更简单、更高效，而将 MOF 用作纤维吸附剂则为利用 SPME 对这些化合物进行具有挑战性的环境监测提供了一种潜在的替代方法。
