College of Chemical Engineering, Sichuan University, Chengdu 610065, China.
J Chromatogr A. 2012 Jul 20;1247:1-9. doi: 10.1016/j.chroma.2012.05.047. Epub 2012 May 18.
This paper reports the synthesis of hydrophilic-hydrophobic magnetic Fe₃O₄-doped polymeric nanoparticles (MPNP) and its application for preconcentration of polycyclic aromatic hydrocarbons (PAHs) in environmental water samples for ultrahigh performance liquid chromatographic (UHPLC) analysis. The MPNP were prepared from highly charged poly(styrene-divinylbenzene-co-4-vinylbenzenesulfonic acid sodium salt) nanoparticles impregnated with Fe²⁺ via the electrostatic attraction and by microwave heating. The MPNP are relatively uniform in size with an average diameter of 50 nm and have a magnetic saturation value of 24.5 emu/g. The hydrophilic-hydrophobic MPNP could easily disperse in water. The phenyl moieties of MPNP assist the adsorption of PAHs via both hydrophobic and π-π interactions. The separation of the PAHs-adsorbed MPNP from water could be easily achieved by a permanent magnet and the adsorbed PAHs were back extracted into acetonitrile for UHPLC analysis. The UHPLC separation of PAHs is very quick and could be achieved within 1.6 min. Factors affecting the extraction and desorption were investigated in detail. Under the optimum experimental conditions, the recoveries of various PAHs including acenaphthylene, anthracene, fluoranthene, fluorene, phenanthrene, and pyrene in water samples at three different concentrations are 75.7-102.9, 77.8-101.2, 86.3-100.7, 88.5-99.7, 92.0-106.4, and 81.6-98.5%, respectively. The recovery SDs are 0.30-8.20% and the instrumental limits of detection are 10.83-18.53 nM. The proposed technique combining hydrophobic extraction and magnetic separation coupled with UHPLC could provide a fast, convenient and sensitive method for the determination of PAHs in water samples.
本文报道了亲水性-疏水性磁性 Fe₃O₄掺杂聚合物纳米粒子（MPNP）的合成及其在环境水样中多环芳烃（PAHs）的预浓缩中的应用，用于超高效液相色谱（UHPLC）分析。MPNP 是通过静电吸引和微波加热，由高电荷聚苯乙烯-二乙烯基苯-共-4-乙烯基苯磺酸纳纳米粒子浸渍 Fe²⁺制备而成。MPNP 粒径较为均匀，平均直径为 50nm，磁饱和值为 24.5emu/g。亲水性-疏水性 MPNP 可轻易分散于水中。MPNP 的苯环结构通过疏水和π-π相互作用辅助 PAHs 的吸附。通过永磁体可轻易实现吸附有 PAHs 的 MPNP 与水的分离，并用乙腈将吸附的 PAHs 反萃取出来，用于 UHPLC 分析。PAHs 的 UHPLC 分离非常迅速，可在 1.6min 内完成。详细考察了影响萃取和解吸的各种因素。在最佳实验条件下，水中不同浓度的苊、蒽、荧蒽、芴、菲和芘的回收率分别为 75.7-102.9%、77.8-101.2%、86.3-100.7%、88.5-99.7%、92.0-106.4%和 81.6-98.5%。回收率的标准偏差为 0.30-8.20%，仪器检出限为 10.83-18.53nM。该技术结合疏水性萃取和磁性分离与 UHPLC 联用，为水样中 PAHs 的测定提供了一种快速、方便、灵敏的方法。
