Novel Imprinted Polymer for the Preconcentration of Cadmium with Determination by Inductively Coupled Plasma Mass Spectrometry

ABSTRACT

A novel Cd(II)-imprinted polymer was prepared with chemical immobilization using N-methacryloyl-L-Histidine as a vinylated chelating agent for online solid-phase extraction of Cd(II) for determination by inductively coupled plasma mass spectrometry. The Cd(II)–monomer complex was synthesized and copolymerized through bulk polymerization method in the presence of ethyleneglycoldimethacrylate cross-linker. The resulting polymer was leached with 1.0 mol L⁻¹ HNO₃ to generate the cavities in the polymer for Cd(II) ions. The experimental conditions, including load pH, solution flow rate, and eluent concentration for effective sorption of Cd(II), were optimized using a minicolumn of the imprinted polymer. A volume of 5.0 mL sample 5 µg L⁻¹ Cd(II) solution at pH 6.5 was loaded on the column at 2.0 mL min⁻¹ using a sequential injection system followed by elution with 1.0 mL of 0.75 mol L⁻¹ HNO₃. The relative selectivity coefficients of the imprinted polymer for Cd(II) were 38.5, 3.5, 3.0, 2.5, and 6.0 in the presence of Cu(II), Ni(II), Zn(II), Co(II), and Pb(II), respectively. Computational calculations revealed that the selectivity of the imprinted polymer was mediated by the stability of Cd(II)–N-methacryloyl-L-Histidine complex which was more stable than commonly used monomers including 4-vinyl pyridine, methacrylic acid, and vinylimidazole. The detection limit and relative standard deviation were 0.004 µg L⁻¹ and 3.2%, respectively. The method was validated by the analysis of seawater certified reference material (CASS-4) and successfully used for the determination of Cd(II) in coastal seawater and estuarine water.

KEYWORDS:

• Cadmium
• chemical immobilization
• inductively coupled plasma mass spectrometry
• ion-imprinted polymer
• solid-phase extraction