Selective Removal of the Genotoxic Compound 2-Aminopyridine in Water using Molecularly Imprinted Polymers Based on Magnetic Chitosan and β-Cyclodextrin
Abstract
:1. Introduction
2. Materials and Methods
2.1. Reagents and Chemicals
2.2. Synthesis of Magnetic Chitosan Imprinted Polymer
2.2.1. Synthesis of Fe3O4-Chitosan Particles
2.2.2. Synthesis of Fe3O4-CTs@MIP
2.3. Synthesis of Magnetic β-Cyclodextrin Imprinted Polymer
2.3.1. Synthesis of MAH-β-CD
2.3.2. Synthesis of MAH-β-CD Polymer Coated Magnetic Particles
2.3.3. Synthesis of Fe3O4-MAH-β-CD@MIP
2.4. Characterization
2.5. Adsorption Experiments
2.6. Selective Adsorption
2.7. Influence of Coexistent Ions
2.8. The Contrast of MMIPs and Activated Carbon in Selective Adsorption Performance
2.9. Regeneration and Reusable Studies
2.10. Removal of 2-Aminopyridine from Different Water Samples
3. Results and Discussion
3.1. NMR Analysis of MAH-β-CD
3.2. Characterization of the Magnetic Fe3O4-CTs@MIP and Fe3O4-MAH-β-CD@MIP
3.3. Adsorption Study
3.3.1. Effect of Solution pH on Adsorption
3.3.2. Adsorption Isotherm
3.4. Adsorption Kinetics
3.5. Adsorption Thermodynamics
3.6. Selective Adsorption
3.7. Influence of Coexistent Ions
3.8. Comparison of MIPs and Activated Carbon in Selective Adsorption Performance
3.9. Regeneration and Reusable Studies
3.10. Removal of 2-Aminopyridine with MMIPs in Different Water Samples
4. Conclusions
Supplementary Materials
Acknowledgments
Author Contributions
Conflicts of Interest
References
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Polymer | Langmuir Isotherm | R2 | Freundlich Isotherm | R2 | ||
---|---|---|---|---|---|---|
Qm (mg·g−1) | KL (mL·mg−1) | KF (mg1-1/n·mL1/n·g−1) | 1/n | |||
Fe3O4-CTs@MIP | 39.22 ± 1.466 | 7.29 ± 0.682 | 0.998 | 64.22 ± 3.316 | 0.678 ± 0.0392 | 0.981 |
Fe3O4-CTs@NIP | 19.88 ± 0.577 | 6.29 ± 0.414 | 0.998 | 28.51 ± 1.353 | 0.655 ± 0.0326 | 0.987 |
Fe3O4-MAH-β-CD@MIP | 46.51 ± 1.314 | 10.24 ± 0.634 | 0.996 | 81.85 ± 3.797 | 0.629 ± 0.0277 | 0.989 |
Fe3O4-MAH-β-CD@NIP | 22.52 ± 0.823 | 6.94 ± 0.483 | 0.997 | 33.11 ± 2.113 | 0.641 ± 0.0468 | 0.987 |
Adsorbents | Target | Qm (mg·g−1) | References |
---|---|---|---|
Bulk polymerized imprinted polymer | 2-aminopyridine | 12.8 | [16] |
Hybrid MIP with NIPA hydrogel | 4-aminopyridine | 6.0 | [27] |
MIH-FRP hydrogel | 3-aminopyridine | 600.0 | [36] |
Magnetic chitosan-based imprinted polymer | 2-aminopyridine | 39.2 | This study |
Magnetic β-cyclodextrin based imprinted polymer | 2-aminopyridine | 46.5 | This study |
MIPs | Adsorption Capacity (Qe, mg·g−1) of Fe3O4-CTs@MIP | Adsorption Capacity (Qe, mg·g−1) of Fe3O4-MAH-β-CD@MIP |
---|---|---|
Batch#1 | 9.28 | 12.19 |
Batch#2 | 10.04 | 12.65 |
Batch#3 | 8.71 | 14.06 |
Average ± SD | 9.34 ± 0.657 | 12.97 ± 0.978 |
Adsorption Isotherm Models | Constants | Fe3O4-CTs@MIP | Fe3O4-MAH-β-CD@MIP | ||||||||
---|---|---|---|---|---|---|---|---|---|---|---|
288 K | 298 K | 308 K | 318 K | 328 K | 288 K | 298 K | 308 K | 318 K | 328 K | ||
Langmuir isotherm | Qm (mg·g−1) | 41.32 ± 1.917 | 39.22± 1.466 | 34.60 ± 0.977 | 30.68 ± 0.872 | 27.25 ± 0.967 | 48.78 ± 1.737 | 46.51 ± 1.374 | 41.67 ± 1.407 | 37.45 ± 1.139 | 33.56 ± 0.854 |
KL (mL·mg−1) | 8.3 ± 0.591 | 7.29 ± 0.682 | 5.67 ± 0.375 | 4.87 ± 0.297 | 4.32 ± 0.268 | 12.81 ± 0.908 | 10.24 ± 0.634 | 7.27 ± 0.481 | 5.68 ± 0.339 | 4.89 ± 0.289 | |
R2 | 0.998 | 0.998 | 0.998 | 0.998 | 0.998 | 0.994 | 0.996 | 0.998 | 0.999 | 0.999 | |
Freundlich isotherm | KF (mg1-1/n·mL1/n·g−1) | 69.86 ± 3.474 | 64.22 ± 3.316 | 53.06 ± 3.285 | 44.59 ± 2.701 | 37.82 ± 2.276 | 87.42 ± 3.474 | 81.85 ± 3.797 | 68.16 ± 4.349 | 57.29 ± 3.598 | 48.68 ± 2.887 |
1/n | 0.66 ± 0.0482 | 0.678 ± 0.0392 | 0.71 ± 0.0519 | 0.72 ± 0.0517 | 0.74 ± 0.0511 | 0.59 ± 0.0482 | 0.63 ± 0.0277 | 0.68 ± 0.0497 | 0.70 ± 0.0507 | 0.72 ± 0.0481 | |
R2 | 0.981 | 0.981 | 0.982 | 0.982 | 0.982 | 0.989 | 0.989 | 0.988 | 0.988 | 0.988 |
Polymers | T (K) | Thermodynamic Parameters | R2 | ||
---|---|---|---|---|---|
ΔG (kJ·mol−1) | ΔH (kJ·mol−1) | ΔS (J·mol−1·k−1) | |||
Fe3O4-CTs@MIP | 288 | −2.81 | −11.26 | −29.31 | 0.991 |
298 | −2.64 | −28.89 | |||
308 | −2.23 | −29.28 | |||
318 | −1.94 | −29.29 | |||
328 | −1.70 | −29.12 | |||
Fe3O4-MAH-β-CD@MIP | 288 | −3.76 | −16.14 | −42.98 | 0.990 |
298 | −3.47 | −42.50 | |||
308 | −2.85 | −43.15 | |||
318 | −2.44 | −43.08 | |||
328 | −2.13 | −42.69 |
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Zhang, W.; Zhu, Z.; Zhang, H.; Qiu, Y. Selective Removal of the Genotoxic Compound 2-Aminopyridine in Water using Molecularly Imprinted Polymers Based on Magnetic Chitosan and β-Cyclodextrin. Int. J. Environ. Res. Public Health 2017, 14, 991. https://doi.org/10.3390/ijerph14090991
Zhang W, Zhu Z, Zhang H, Qiu Y. Selective Removal of the Genotoxic Compound 2-Aminopyridine in Water using Molecularly Imprinted Polymers Based on Magnetic Chitosan and β-Cyclodextrin. International Journal of Environmental Research and Public Health. 2017; 14(9):991. https://doi.org/10.3390/ijerph14090991
Chicago/Turabian StyleZhang, Wei, Zhiliang Zhu, Hua Zhang, and Yanling Qiu. 2017. "Selective Removal of the Genotoxic Compound 2-Aminopyridine in Water using Molecularly Imprinted Polymers Based on Magnetic Chitosan and β-Cyclodextrin" International Journal of Environmental Research and Public Health 14, no. 9: 991. https://doi.org/10.3390/ijerph14090991