State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry & Chemical Engineering and Center of Materials Analysis, Nanjing University, 163 Xianlin Avenue, Nanjing, 210023, China.
Technical Center for Industrial Product and Raw Material Inspection and Testing, Shanghai Customs, Shanghai, 200135, China.
Mikrochim Acta. 2020 May 28;187(6):356. doi: 10.1007/s00604-020-04329-0.
The preparation of an amino-functionalized hybrid monolithic column (TEOS-co-AEAPTES) via one-pot co-condensation of tetraethoxysilane (TEOS) and N-(β-aminoethyl)-γ-aminopropyltriethoxysilane (AEAPTES) in a capillary is descibed. It was used as solid-phase microextraction (SPME) matrix followed by inductively coupled plasma-mass spectrometry (ICP-MS) for determination of trace metals. Under optimum conditions, the amino-functionalized SPME material can simultaneously retain Cu(II), Zn(II), Au(III), and Pb(II) with adsorption capacities of 148, 60, 81, and 64 μg m, respectively. Subsequently, these four metal ions can be quantitatively eluted using 1 mol L HNO containing 1% thiourea. The retention mechanism of Cu(II), Zn(II), Au(III), and Pb(II) on the amino-functionalized hybrid monolith was explained as the combination of electrostatic and coordination interactions. With a 10-fold enrichment factor, the calibration curves were established in the range 0.5-100 μg L with linear correlation coefficients above 0.9943 and the limits of quantitation were 0.05 μg L for four target analytes. The limits of detection were 0.006, 0.012, 0.004, and 0.007 μg L for Cu(II), Zn(II), Au(III), and Pb(II), respectively. The protocol was validated by analyzing Certified Reference Materials including standard sediment, soil, and nickel ore, and the results were in good agreement with their certified values. The relative standard deviations of the method were in the range 0.22-17.6%. The recoveries of the four metal ions in spiked samples were in the range 88.0-113.8%. Compared to direct ICP-MS determination, the proposed in-tube SPME procedure can effectively eliminate the interference from complex matrix, especially from those ores with very high content of main metal to improve the accuracy of analysis. Therefore the method is suitable for the simultaneous determination of ultra-trace Cu(II), Zn(II), Au(III), and Pb(II) in environmental and mineral samples. Graphical abstract The preparation of the TEOS-co-AEAPTES monolithic column and the SPME procedure of Cu(II), Zn(II), Au(III), and Pb(II).
通过在毛细管中一步共缩合四乙氧基硅烷（TEOS）和 N-(β-氨乙基)-γ-氨丙基三乙氧基硅烷（AEAPTES），制备了一种氨基功能化的混合整体柱（TEOS-co-AEAPTES）。它被用作固相微萃取（SPME）基质，然后通过电感耦合等离子体质谱（ICP-MS）测定痕量金属。在最佳条件下，氨基功能化的 SPME 材料可以同时保留 Cu(II)、Zn(II)、Au(III)和 Pb(II)，其吸附容量分别为 148、60、81 和 64μg m。随后，使用含有 1%硫脲的 1 mol L HNO 可以定量洗脱这四种金属离子。Cu(II)、Zn(II)、Au(III)和 Pb(II)在氨基功能化混合整体柱上的保留机理解释为静电和配位相互作用的结合。在 10 倍富集因子下，在 0.5-100μg L 范围内建立了校准曲线，相关系数均大于 0.9943，四种目标分析物的定量限为 0.05μg L。Cu(II)、Zn(II)、Au(III)和 Pb(II)的检出限分别为 0.006、0.012、0.004 和 0.007μg L。通过分析包括标准沉积物、土壤和镍矿石在内的认证参考材料验证了该方案，结果与认证值吻合良好。该方法的相对标准偏差在 0.22-17.6%之间。四种金属离子在加标样品中的回收率在 88.0-113.8%之间。与直接 ICP-MS 测定相比，提出的管内 SPME 程序可以有效消除复杂基质的干扰，特别是那些主金属含量非常高的矿石的干扰，从而提高分析的准确性。因此，该方法适用于环境和矿物样品中超痕量 Cu(II)、Zn(II)、Au(III)和 Pb(II)的同时测定。
Zotero 插件