Liu Wan-Ling, Lirio Stephen, Yang Yicong, Wu Lin-Tai, Hsiao Shu-Ying, Huang Hsi-Ya
Department of Chemistry, Chung Yuan Christian University, 200 Chung Pei Road, Chung-Li 320, Taiwan.
Department of Chemistry, Chung Yuan Christian University, 200 Chung Pei Road, Chung-Li 320, Taiwan; Institute of Modern Separation Science, Northwest University, Xi'an 710069, China.
J Chromatogr A. 2015 May 22;1395:32-40. doi: 10.1016/j.chroma.2015.03.066. Epub 2015 Mar 31.
In this study, an organic polymer monolithic columns, which were prepared via in situ polymerization of alkyl methacrylate-ester (AMA), divinylbenzene (DVB) and vinylbenzyl trimethylammonium chloride (VBTA, charged monomer), were developed as adsorbent for solid-phase microextraction (SPME). Different parameters affecting the extraction efficiency for nine (9) non-steroidal anti-inflammatory drugs (NSAIDs) such as the ratio of the stearyl methacrylate (SMA) to DVB monomer, column length, sample pH, extraction flow rate and desorption solvent were investigated to obtain the optimal SPME condition. Also, the permeability for each poly(AMA-DVB-VBTA) monolithic column was investigated by adding porogenic solvent (poly(ethylene glycol), PEG). Using the optimized condition, a series of AMA-based poly(AMA-DVB-VBTA) monolith columns were developed to determine the effect the extraction efficiency of NSAIDs by varying the alkyl chain length of the methacrylate ester (methyl-, butyl-, octyl-, or lauryl-methacrylate; (MMA, BMA, OMA, LMA)). Results showed that decreasing the AMA chain length increases the extraction efficiency of some NSAIDs (i.e. sulindac (sul), naproxen (nap), ketoprofen (ket) and indomethacin (idm)). Among the poly(AMA-DVB-VBTA) monolithic columns, poly(BMA-DVB-VBTA) showed a highly repeatable extraction efficiency for NSAIDs with recoveries ranging from 85.0 to 100.2% with relative standard deviation (RSD) less than 6.8% (n=3). The poly(BMA-DVB-VBTA) can also be reused for at least 50 times without any significant effect in extraction efficiency for NSAIDs. Finally, using the established conditions, the poly(BMA-DVB-VBTA) was used to extract trace-level NSAIDs (100μgL(-1)) in river water with good recoveries ranging from 75.8 to 90.8% (RSD<14.9%).
在本研究中，通过甲基丙烯酸烷基酯（AMA）、二乙烯基苯（DVB）和乙烯基苄基三甲基氯化铵（VBTA，带电单体）的原位聚合制备的有机聚合物整体柱被开发为用于固相微萃取（SPME）的吸附剂。研究了影响9种非甾体抗炎药（NSAIDs）萃取效率的不同参数，如甲基丙烯酸硬脂酯（SMA）与DVB单体的比例、柱长、样品pH值、萃取流速和解吸溶剂，以获得最佳的SPME条件。此外，通过添加致孔溶剂（聚乙二醇，PEG）研究了每个聚（AMA-DVB-VBTA）整体柱的渗透性。在优化条件下，开发了一系列基于AMA的聚（AMA-DVB-VBTA）整体柱，通过改变甲基丙烯酸酯（甲基-、丁基-、辛基-或月桂基-甲基丙烯酸酯；（MMA、BMA、OMA、LMA））的烷基链长度来确定其对NSAIDs萃取效率的影响。结果表明，缩短AMA链长度可提高某些NSAIDs（即舒林酸（sul）、萘普生（nap）、酮洛芬（ket）和吲哚美辛（idm））的萃取效率。在聚（AMA-DVB-VBTA）整体柱中，聚（BMA-DVB-VBTA）对NSAIDs表现出高度可重复的萃取效率，回收率在85.0%至100.2%之间，相对标准偏差（RSD）小于6.8%（n=3）。聚（BMA-DVB-VBTA）还可重复使用至少50次而对NSAIDs的萃取效率无任何显著影响。最后，在既定条件下，使用聚（BMA-DVB-VBTA）萃取河水中痕量水平的NSAIDs（100μg L⁻¹），回收率良好，在75.8%至90.8%之间（RSD<14.9%）。
