| 摘要: | 基於能擴展 MALDI-TOF-MS 在小分子領域的應用，及對其能廣泛使用於檢測防曬產品中的二苯甲酮類化合物在環境中的殘留，與對人體及生態環境造成危害的擔憂，本研究利用對環境友善的無溶劑法合成金屬有機骨架材料(Metal Organic Frameworks, MOFs)MIL-101(Cr)並將其作為MALDI-TOF-MS檢測環境水樣中二苯甲酮類化合物殘留的吸附劑及基質，藉由減少脫附過程及 MALDI-TOF-MS 樣品消耗低、檢測速度快等特性開發出的新穎檢測方法。
藉由針對吸附劑用量、萃取時間、水樣酸鹼值、使用分散溶劑這四個條件進行萃取條件的優化，以提升檢測效果。
本研究方法中對四種待測物的檢量線濃度範圍介於 0.020-0.2 mM 之間，偵測極限均介於 0.0010-0.0013 mM 之間，R2≥0.9674 且精密度 RSD≤6%，認證此方法具有良好的線性關係及精密度。在實際應用於環境水樣中的萃取回收率均介於 67％-96%之間，相對標準偏差皆小於 6%，顯示方法具有良好的回收率及低的基質干擾。
簡而言之，本研究方法開發出了結合 MALDI-TOF-MS 的快速檢測環境水樣中防曬劑成分二苯甲酮類化合物殘留的方法，成功擴大MALDI-TOF-MS在小分子方面的應用。
;To expand the applications of matrix-assisted laser desorption/ ionization time-of-flight mass spectrometry (MALDI-TOF-MS) in the field of small molecules detection, in this study, we successfully synthesized metal organic frameworks (MOFs) MIL-101 (Cr) by solvent-free method, and applied MIL-101 (Cr) as the adsorbent for dispersive micro solid-phase extraction (DmSPE), and then, the MIL-101 can be directly applied as matrix for MALDI-TOF-MS to determine benzophenones (BPs) residues in environmental water samples. We explore the application of MIL-101 (Cr) as both the adsorbent and matrix for MALDI for the enrichment and analysis of BPs. The developed method reduced the steps of analysis, i.e., no solvent desorption, and speed-up the multi-target analytes detection, i.e., no chromatography.
Four key experimental conditions were evaluated and optimized, such as, the adsorbent amount, extraction time, pH value of water sample, and dispersive solvent used. After
optimization, the limits of detection (LOD) of the method ranged between 0.020-0.2 mM. Precision was evaluated using intra-day and inter-day analyses, with relative standard
deviations (RSD) of all below 6%, and R2 of linearities were large than 0.9674, indicating good repeatability and linear relationship of the method. The extraction recovery rates in real environmental water samples were between 67% and 96%, and the RSD were less than 6%, showing that the method has a good recovery and repeatability rates in environmental water
samples. In short, we developed an analytical method for the rapid detection of BPs residues in environmental water samples by coupling with MOF, DmSPE and MALDI-TOF-MS, and
moreover, successfully expanded the application of MALDI-TOF-MS in small molecules detection. |
