| 摘要: | 本研究之待測物，防曬乳成分–二苯甲酮類化合物(Benzophenones, 簡稱BPs)，此類化合物能夠吸收紫外線作為防曬成分，因此被廣泛應用於個人護理產品、食品包裝塗料等民生用品中，然而BPs屬於內分泌干擾物質(Endocrine disrupting chemicals, 簡稱EDCs )，隨著其使用量的增加，造成的污染範圍也隨之擴展進入到環境中，對環境及人體造成的累積性危害也逐漸受到各方矚目。
因此，開發出一種靈敏度高、簡單、高效，用以檢測環境水樣中六種防曬乳成分殘留，且符合綠色化學之分析方法。本研究以聚離子液體為塗層材料作為攪拌子吸附萃取法中之新穎吸附劑，其具有熔點低、熱穩定性佳、可回收再利用、對環境友善等優點，且具有結構調控性，研究中選擇咪唑型陽離子及PF6-陰離子作為聚合物單體組成，提高吸附劑在水中的穩定性，搭配超高效液相層析儀串聯電灑游離法(+)四極桿飛行時間式質譜儀(UHPLC-ESI(+)-QTOF-MS)，並以高解析汲取離子層析圖模式增加解析度。
實驗條件以單因子最佳化及實驗設計軟體Box-Behnken Design (BBD)，利用BBD中的變異數分析(ANOVA)進行萃取條件最佳化。獲得最佳條件為：以聚離子液體P(C10ImPF6)作為吸附劑塗層，於20 mL水樣中進行吸附90分鐘，攪拌速度600 rpm，脫附溶劑為1 mL甲醇，以Vortex方式脫附1分鐘後，吹氮濃縮至0.1 mL，最後將3 μL萃取物注入 UHPLC-QTOF-MS 進行檢測分析，濃縮倍率達200倍，提高分析靈敏度。
本研究所開發之方法P(C10ImPF6)-SBSE，偵測極限LOD為0.025至3 ng/mL，Intra day及Inter day的相對標準偏差RSD ≤ 4%，萃取回收率介於93% 至104%之間，由結果可知本方法呈現良好穩定性及再現性。最後以P(C10ImPF6)-SBSE結合UHPLC-ESI(+)-QTOF-MS進行真實環境水樣中防曬乳成分殘留之檢測，包括校內百花川及中大湖、南崁溪上下游，成功檢測待測物BP-3之殘留。;In this study, benzophenone-type (BPs) ultraviolet (UV)-filters are used as the analysis object, which can absorb UV radiation as sunscreen ingredients, so they are widely used in personal care products, food-packed coatings and other household products. However, BPs belong to endocrine disrupting chemicals (EDCs), with the increase of their usage, the scope of contaminants will also expand into the environment. They have also gradually attracted much public attention of all parties, due to the cumulative harm to the ecosystems and human body.
Therefore, a high-sensitivity, simple, and efficient analytical method for detecting the residues of six BPs UV-filters in environmental water samples, which comply with developed green chemistry. In this study, polyionic liquid (PIL) was used as the coating material as a novel adsorbent in the stir bar sorptive extraction (SBSE) method, which has the advantages of low melting point, good thermal stability, recyclability, structure controllability and environmental friendliness. Imidazolium cation and (PF6-) hexafluorophosphate anion as a polymer monomer composition, improve the stability of the adsorbent in water. Ultra-high performance liquid chromatography and electrospray ionization(+)-quadrupole time-of-flight mass spectrometry (UHPLC-ESI(+)-QTOF-MS) was applied for detection and quantitation coupled with high-resolution extracted ion chromatogram mode to increase the sensitivity.
The experimental conditions were optimized by one-factor at-a-time optimization and multivariate experimental design software Box-Behnken Design (BBD), and the extraction conditions were optimized by using the analysis of variance (ANOVA) in BBD. The best conditions were as follows: P(C10ImPF6) was used as the adsorbent coating, extracted in 20 mL water sample for 90 min, the stirring rate was 600 rpm, the desorption solvent was 1 mL methanol, and the desorption time was 1 min. Then, the extract was nitrogen sweeping to 0.1 mL, and finally 3 μL of the extract was directly injected into UHPLC-QTOF-MS for detection. The enrichment factor can be reached at 200-fold, which enhanced the analysis sensitivity.
The developed method P(C10ImPF6)-SBSE exhibited satisfactory linearity (R2 > 0.9957), favorable precision with Intra day and Inter day relative standard deviation (RSD%) were all less than 4%, and a limit of detection (LOD) ranging from 0.025 to 3 ng/mL, satisfactory extraction recovery ranging from 93% to 104%, the results show that the method presents good stability and reproducibility. Finally, the developed P(C10ImPF6)-SBSE method combined with UHPLC-ESI(+)-QTOF-MS was then successfully applied to detect BPs residues in environmental water samples. |
