2011 水中多羟基富勒烯的鉴定以及液相四级杆质谱定量分析 Characterization and Liquid Chromatography-MSM.pdf

Published: February 04, 2011 r 2011 American Chemical Society 1777 /10.1021/ac1031379 |Anal. Chem. 2011, 83, 1777–1783 ARTICLE /ac Characterization and Liquid Chromatography-MS/MS Based Quantification of Hydroxylated Fullerenes Tzu-Chiao Chao,?,?,§ Guixue Song,? Nicole Hansmeier,§ Paul Westerhoff,? Pierre Herckes,? and Rolf U. Halden*,?,§ ?School of Sustainable Engineering and The Built Environment, ?Department of Chemistry and Biochemistry, and §Center for Environmental Biotechnology, The Biodesign Institute at Arizona State University, Arizona State University, Tempe, Arizona 85287, United States bS Supporting Information ABSTRACT: Highly water-soluble hydroxylated fullerene deriv atives are being investigated for a wide range of commercial products as well as for potential cytotoxicity. However, no analytical methods are currently available for their quantification at sub-ppm concentrations in environmental matrixes. Here, we report on the development and comparison of liquid chroma- tography-ultraviolet/visible spectroscopy (LC-UV/vis) and liquid chromatography-mass spectrometry (LC-MS) based detection and quantification methods for commercial fullerols. We achieved good separation efficiency using an amide-type hydrophilic interaction liquid chromatography (HILIC) col- umn (plate number 2000) under isocratic conditions with 90% acetonitrile as the mobile phase. The method detection limits (MDLs) ranged from 42.8 ng/mL (UV detection) to 0.19 pg/mL (using MS with multiple reaction monitoring, MRM). Other MS measurement modes achieved MDLs of 125 pg/mL (single quad scan, Q1) and 1.5 pg/mL (multiple ion monitoring, MI). Each detection method exhibited a good linear response over several orders of magnitude. Moreover, we tested the robustness of these methods in the presence of Suvanee River fulvic acids (SRFA) as an example of organic matter commonly found in environmental water samples. While SRFA significantly interfered with UV- and Q1-based quantifications, the