Study On Separation And Analysis Of Functional β - Cyclodextrin Polymer By Solid Phase Extraction

Solid phase extraction (SPE) is an effective of pretreatment technology commonly used in enrichment and separation, which has advantages of good selectivity, effective separation of interference, high enrichment factor, simple operation, low environmental pollution. Functionalized β-cyclodextrin cross-linked polymer as a new type of supramolecular materials, not only retain the hydrophobic cavity of the skeleton of cyclodextrin molecule, but also modify group could enhance its functionality and its performance was better than its parent. The important properties of ionic liquids (ILs) include extremely low volatility, non-flammability, high thermal stability, allowing fine-tuning of the ILs properties for specific applications. And for these reasons, ionic liquid can be used as a functional groups to improve the extraction performance of cyclodextrin. Herein, in this study P-CD was functionalized using a-picoline and further cross-linked with the HDI to form insoluble polymer (ILs-P-CDCP) for wider applications. At the same time, magnetic nanomaterials Fe3O4@ILs-β-CDCP was synthesized further. ILs-β-CDCP and Fe3O4@ILs-β-CDCP as new type of solid phase extraction materials were applied into the separation/analysis of target analyte. The major contents of this paper are described as follows:1. a-picoline ionic liquid-β-cyclodextrin polymer for the separation/analysis of Allura Red in foodsa-picoline ionic liquid-β-cyclodextrin polymer (ILs-β-CDCP) was firstly synthesized using functionalized β-cyclodextrin (β-CD) with a-picoline and was further polymerized using hexamethylene diisocyanate (HDI) linker to form insoluble ILs-β-CDCP. We established a new method of solid phase extraction (SPE) coupled with high-performance liquid chromatography for separation/analysis of Allura red in foods. ILs-β-CDCP showed a higher adsorption capacity toward Allura Red in water than β-CDCP. Allura Red was adsorbed rapidly by ILs-β-CDCP (adsorption efficiency:99%) and eluanted by Ethanol-ammonia-water (7:2:1) (elution efficiency: 100%) at room temperature. Under the optimal conditions, precuucentration factor of the proposed method was 14-fold. The linear range, detection limit (DL), correlation coefficient (R2) and relative standard deviation (RSD) were found to be 5.0-2.5×104 μg L-1,0.35 g L-1,0.9985 and 0.47%(n=3, c=5.0μg mL-1), respectively. ILs-P-CDCP can be used repeatedly for 13 times. This proposed method had been successfully applied to the determination of Allura Red in real samples.2. a-picoline ionic liquid-β-cyclodextrin polymer for the separation/analysis of lornoxicam in serum and tablet samplesA novel method of solid phase extraction (SPE) coupled with UV-Vis spectrophotometry for separation/analysis of lornoxicam was established. ILs-β-CDCP showed a higher adsorption capacity toward lornoxicam than β-CDCP. lornoxicam was adsorbed rapidly by ILs-β-CDCP (adsorption efficiency:92%) and eluanted by methanol(elution efficiency:99%) at room temperature. Under the optimal conditions, preconcentration factor of the proposed method was 15-fold. The linear range, correlation coefficient (R2), detection limit (DL) and relative standard deviation(RSD) were found to be 2.0-4.0×104 μg L-1,0.9962,0.19 μg L-1 and 0.33%(n=3, c=5.0 μg mL-1), respectively. ILs-β-CDCP can be used repeatedly for 6 times. This proposed method had been successfully applied to the determination of lornoxicam in serum and tablet samples.3. Solid phase extraction coupled with ICP-OES for the separation/analysis of Mn(Ⅱ) and Mn(Ⅶ) in waterIonic liquid-β-cyclodextrin polymer (ILs-β-CDCP) was coated Fe3O4 nanoparticles to prepare magnetic solid phase extraction agent (Fe3O4@ILs-β-CDCP)and establish a new method of magnetic solid phase extraction (MSPE) coupled with ICP-OES for separation/analysis of Mn(Ⅱ) and Mn(VII) in water. Fe3O4@ILs-β-CDCP was characterized with FTIR,13C CP/MAS NMR, XRD, TGA and SEM. Fe3O4@ILs-β-CDCP showed a higher adsorption capacity toward Mn(Ⅱ) and Mn(VII). Several factors, such as the pH value, extraction temperature, extraction time were optimized to achieve the best extraction efficiency. The results showed that Mn(Ⅶ) could be extracted quantitatively and rapidly in pH range of 6.00-11.00 at room temperature. But Mn(Ⅱ) could not be extracted quantitatively in pH range of 3.00-7.00. Mn(II) and Mn(Ⅶ) were eluanted within 2 min with 2.00 mL HCl (1 mol mL-1, elution efficiency:100%) at room temperature. Fe3O4@ILs-β-CDCP exhibited favorable performance toward Mn(II) and Mn(Ⅶ) from standard water, tap water, lake water and mineral water. The experimental results herein suggested that Fe3O4@ILs-P-CDCP could be successfully applied in real samples.4. Solid phase extraction coupled with HPLC for the separation/analysis of Congo Red in water and food.A novel method of solid phase extraction (MSPE) coupled with HPLC for the separation/analysis of lornoxicam was established. The results showed that:Congo Red could be extracted quantitatively (adsorption efficiency:95%) by Fe3O4@ILs-β-CDCP at room temperature. Congo Red were eluanted within 2 min with 3.00 mL ethanol (elution efficiency: 100%) at room temperature. Under the optimum experimental conditions, the preconcentration factor of the proposed method was 20-fold. The linear range, correlation coefficient (R2), detection limit (DL) and relative standard deviation(RSD) were found to be 5.0×10-3-1.0×102 μg mL-1,0.9910,1.80 μg L-1 and 0.61%(n=3, c=5.0 μg mL-1), respectively. The proposed method had been successfully applied to determination of Congo Red (recovery:95.2-108.0%) in water and food and the results was satisfactory.