Ho Tien D, Toledo Bruna R, Hantao Leandro W, Anderson Jared L
Department of Chemistry and Biochemistry, The University of Toledo, Toledo, OH 43606, USA.
Department of Chemistry and Biochemistry, The University of Toledo, Toledo, OH 43606, USA; Institute of Chemistry, State University of Campinas (Unicamp), Campinas, São Paulo 13083-907, Brazil.
Anal Chim Acta. 2014 Sep 16;843:18-26. doi: 10.1016/j.aca.2014.07.034. Epub 2014 Jul 24.
Super elastic nitinol (NiTi) wires were exploited as highly robust supports for three distinct crosslinked polymeric ionic liquid (PIL)-based coatings in solid-phase microextraction (SPME). The oxidation of NiTi wires in a boiling (30%w/w) H2O2 solution and subsequent derivatization in vinyltrimethoxysilane (VTMS) allowed for vinyl moieties to be appended to the surface of the support. UV-initiated on-fiber copolymerization of the vinyl-substituted NiTi support with monocationic ionic liquid (IL) monomers and dicationic IL crosslinkers produced a crosslinked PIL-based network that was covalently attached to the NiTi wire. This alteration alleviated receding of the coating from the support, which was observed for an analogous crosslinked PIL applied on unmodified NiTi wires. A series of demanding extraction conditions, including extreme pH, pre-exposure to pure organic solvents, and high temperatures, were applied to investigate the versatility and robustness of the fibers. Acceptable precision of the model analytes was obtained for all fibers under these conditions. Method validation by examining the relative recovery of a homologous group of phthalate esters (PAEs) was performed in drip-brewed coffee (maintained at 60 °C) by direct immersion SPME. Acceptable recoveries were obtained for most PAEs in the part-per-billion level, even in this exceedingly harsh and complex matrix.
超弹性镍钛（NiTi）丝被用作固相微萃取（SPME）中三种不同的基于交联聚合离子液体（PIL）涂层的高稳健支撑体。将NiTi丝在沸腾的（30%w/w）过氧化氢溶液中氧化，随后在乙烯基三甲氧基硅烷（VTMS）中进行衍生化，使得乙烯基部分连接到支撑体表面。乙烯基取代的NiTi支撑体与单阳离子离子液体（IL）单体和双阳离子IL交联剂进行紫外引发的纤维上共聚，生成了一个与NiTi丝共价连接的基于交联PIL的网络。这种改变减轻了涂层从支撑体上的回缩现象，而在未改性的NiTi丝上应用类似的交联PIL时会观察到这种回缩现象。应用了一系列苛刻的萃取条件，包括极端pH值、预先暴露于纯有机溶剂以及高温，以研究纤维的通用性和稳健性。在这些条件下，所有纤维对模型分析物都获得了可接受的精密度。通过直接浸入式SPME，在滴滤咖啡（保持在60°C）中通过检查一组邻苯二甲酸酯（PAE）同系物的相对回收率进行方法验证。即使在这种极其苛刻和复杂的基质中，大多数PAE在十亿分之一水平也获得了可接受的回收率。
