This work proposes a preconcentration method using an ion imprinted polymer (IIP) for determination of cadmium, in several samples, employing a mini-column filled with the polymer coupled into a flow injection analysis system with detection by thermospray flame furnace atomic absorption spectrometry (FIA-TS-FF-AAS). The polymer was synthesized via bulk using methacrylic acid and vinylimidazole as a functional monomer. For the FIA system initial assessment, the variables: pH, eluent concentration and buffer concentration were studied, employing a 23 full factorial design. To obtain the optimum values for each significant variable, a Doehlert matrix was employed. After the optimization conditions as: pH 5.8, eluent (HNO3) concentration of 0.48 mol L and buffer concentration of 0.01 mol L, were adopted. The proposed method showed a linear response in the range of 0.081-10.0 μg L, limits detection and quantification of 0.024 and 0.081 μg L, respectively; preconcentration factor of 165, consumptive index of 0.06 mL, concentration efficiency 132 min, and frequency of readings equal to 26 readings h The accuracy was checked by analysis of certified reference materials for trace metals and recovery tests. The obtained results were in agreement with 95% confidence level (t-test). The method was adequate to apply in samples of: jewelry (earrings) (2.38 ± 0.28 μg kg), black tea (1.09 ± 0.15 μg kg), green tea (3.85 ± 0.13 μg kg), cigarette tobacco (38.27 ± 0.22 μg kg), and hair (0.35 ± 0.02 μg kg).
Restricted access molecularly imprinted polymers (RAMIPs) have been efficiently used for the extraction of small organic molecules from untreated biological matrices (e.g. blood, plasma, serum, and milk). These materials have been obtained by modifying the external surface of conventional molecularly imprinted polymers (MIPs) with hydrophilic monomer grafting, crosslinked protein capsule or a combination of both. These sorbents aggregate the selectivity of MIPs with the ability to exclude macromolecules of restricted access materials (RAMs), being widely employed in solid phase extraction techniques, beyond their use in sensors. In this review, we discuss about the design and application of RAMIPs in biological sample preparation, emphasizing the future trends and remaining challenges of this technology for bioanalyses.
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