富勒烯於環境水體分析方法之建立

Abstract

富勒烯 (fullerene)，泛指以碳元素為主所構成之球形化合物及其相關衍生物之統稱，為奈米碳微粒的一種，由於其獨特的物化特性近幾年開始廣泛應用於醫藥、保養品及光電產業中，因而學者們對於fullerenes於環境中的分布情形及對生物所造成的影響開始重視。目前研究大多針對水體環境中之fullerenes，而吸附於懸浮微粒上之情況較少有文獻進行探討，且偵測極限未能達到ng/L程度，以至於難以分析到環境中的fullerenes。本研究之目的為針對其中五種於各領域較常被應用之fullerenes (fullerene-C60 (C60)、fullerene-C70 (C70)、N-methylfullero- pyrrolidine (MFP)、[6,6]-phenyl C61 butyric acid methyl ester (PCBM) 以及1’,1’’,4’,4’’-tetrahydro-di[1,4]methanonaphthaleno[1,2:2’,3’,56,60:2’’,3’’][5,6] fullerene- C60 (ICBA)) 建立其於環境水體中之分析方法，並同時檢測分散於水體與吸附於懸浮微粒中之fullerenes。高效能液相層析串聯質譜儀分析方法先經由改變其多重反應監測模式參數、離子源模式、層析管柱以及動相比例等以達到最佳儀器分析方法，萃取方法則是先將超音波輔助分散式液液微萃取法、液相-液相萃取法之樣品體積、萃取液體積、分散劑添加以及萃取時間等各項萃取進行最佳化後再選擇較佳之萃取方法，結果顯示以高效能液相層析串聯質譜儀搭配大氣壓化學游離模式，並在甲苯/甲醇之動相比例為50/50 (v/v) 下有最佳分析圖譜與訊號表現。其前處理之萃取方法則以液相-液相萃取法有最佳之萃取效果，C60、C70、MFP、PCBM及ICBA在萃取去離子水樣、河川水樣、醫院放流水以及污水處理廠放流水四種水樣之絕對回收率介於83.2~90.6%、76.3~87.2%、35.9~68.0% 、69.1~85.1%以及87.3~112.1%之間，其相對標準偏差皆落在13% 以內。除了PCBM在回收率與相對標準偏差表現較差以外，其餘目標污染物回收率皆在80~120%良好表現範圍內。最佳化方法偵測極限可達ng/L等級，五種fullerenes分別為25 ng/L、35~40 ng/L、25 ng/L、55 ng/L及25 ng/L。最後本研究可將此最佳化fullerenes分析方法應用於各種廢污水與環境水體中，達到檢測fullerenes的目標。

Fullerenes, an important group of carbon-based nanoparticles, are extensively utilized in medicine, skin care products, and semiconductors. Since it’s widely used, the environmental occurrence and the biological effects of fullerenes were investigated by the scientists; however, the concentration of fullerenes in environment is at ng/L level, which causes difficulties for determination. In addition, most of the studies focus on fullerenes that were suspended in liquid rather than attached on suspended solids. In this study, high performance liquid chromatography tandem mass spectrometry coupled with atmospheric pressure chemical ionization was used to identify and quantitate five fullerenes including fullerene-C60 (C60), fullerene-C70 (C70), N-Methylfulleropyrrolidine (MFP), [6,6]-Phenyl C61 butyric acid methyl ester (PCBM) and 1’,1’’,4’,4’’-Tetrahydro-di[1,4]methanonaphthaleno[1,2:2’,3’,56,60: 2’’,3’’][5,6] fullerene-C60 (ICBA) in environmental water samples. HPLC analytical method was optimized by several parameters: multiple reaction monitoring (MRM) transition, ion sources, columns and mobile phase ratio. Extraction method was adjust by sample volume, extraction solvent volume, addition of dispersant and extraction time. The results showed that liquid-liquid extraction (LLE) had better extraction efficiency than ultrasound-assisted dispersive liquid-liquid microextraction (UA-DLLME). The developed method enabled to detect and quantify fullerenes from river water samples, hospital wastewater, and wastewater treatment plant effluents. The method detection limits of C60, C70, MFP, PCBM and ICBA in four different water matrixes were 25 ng/L, 35~40 ng/L, 25 ng/L, 55 ng/L, and 25 ng/L, respectively. And the absolute recoveries were 83.2~90.6%, 76.3~87.2%, 35.9~68.0%, 69.1~85.1%, and 87.3~112.1%, respectively. The relative standard deviations of the extraction method ranged from 1.3%~7.7%, 5.1%~12.1%, 5.2%~8.7%, 14.0%~30.8% and 1.6%~9.3%, respectively. Optimized LLE method was used to detect the occurrence of fullerenes in aqueous environments.