Key Laboratory of Hunan Province for Advanced Carbon-based Functional Materials, School of Chemistry and Chemical Engineering, Hunan Institute of Science and Technology, Yueyang, 414006, Hunan, PR China.
College of Food Science & Technology, Shanghai Ocean University, Shanghai, 201306, Shanghai, China.
Talanta. 2020 Nov 1;219:121175. doi: 10.1016/j.talanta.2020.121175. Epub 2020 May 21.
Headspace solid-phase microextraction (HS-SPME) of low volatile analytes from complex aqueous samples can be substantially facilitated by elevating the temperature of the samples. However, many SPME coatings prepared from novel sorptive materials may suffer from low stabilities in hot water steam. Herein, a superhydrophobic metal-organic framework (MOF) derived from decorating the metal-oxo nodes of the amino-functionalized UiO-66(Zr) with phenylsilane was prepared and successfully developed into a novel SPME fiber coating. The highest extraction efficiencies towards the semi-volatile ultraviolet (UV) filters were achieved when the aqueous samples were heated up to 100 °C. It was notable that the lab-made coating exhibited extraordinary stability towards hot water steam, probably because the hydrophobic groups capped on the MOF prevented water molecules from entering and deconstructing its lattice. Even after being treated with water steam under 100 °C for 21 h, the extraction performance of the coating remained unchanged, and the crystal structure of the MOF maintained. Furthermore, a negligible matrix effect was observed even in the samples containing humic acid. Under the optimal extraction and thermal desorption conditions, a method for determining UV filters in aqueous samples was established, which possessed low detection limits (0.6-2.1 ng L), wide linear ranges (10-50000 ng L), good inter-fiber reproducibility (2.3-6.0%, n = 6), and satisfying intra-fiber repeatability (1.8-5.8%, n = 3). The method was successfully applied in quantifying UV filters in environmental water samples. In addition, the lab-made NH-UiO-66(Zr)-shp-coated fiber was also suitable for the analysis of polycyclic aromatic hydrocarbons (PAHs). This study provided an effective strategy for preparing MOF coatings that can maintain their crystalline structures and high extraction performances in high-temperature steam.
升高样品温度可以大大促进从复杂水相样品中萃取低挥发性分析物的顶空固相微萃取（HS-SPME）。然而，许多由新型吸附材料制备的 SPME 涂层在热水蒸汽中可能稳定性较低。在此，通过在氨基功能化的 UiO-66（Zr）的金属-氧节点上修饰苯基硅烷制备了一种超疏水金属有机骨架（MOF），并成功地将其开发成一种新型 SPME 纤维涂层。当将水样品加热至 100°C 时，可实现对半挥发性紫外线（UV）过滤器的最高萃取效率。值得注意的是，该自制涂层对热水蒸汽表现出非凡的稳定性，这可能是因为涂覆在 MOF 上的疏水性基团阻止水分子进入并破坏其晶格。即使在 100°C 下经受 21 小时的水蒸汽处理，涂层的萃取性能仍保持不变，且 MOF 的晶体结构保持不变。此外，即使在含有腐殖酸的样品中也观察到可忽略的基质效应。在最佳萃取和热解吸条件下，建立了一种用于测定水相样品中 UV 过滤器的方法，该方法具有较低的检测限（0.6-2.1ngL）、较宽的线性范围（10-50000ngL）、良好的纤维间重现性（2.3-6.0%，n=6）和令人满意的纤维内重复性（1.8-5.8%，n=3）。该方法成功应用于定量环境水样中的 UV 过滤器。此外，自制的 NH-UiO-66（Zr）-shp 涂层纤维也适用于多环芳烃（PAHs）的分析。该研究为制备在高温蒸汽中保持其晶体结构和高萃取性能的 MOF 涂层提供了一种有效策略。
