Rapid CE-UV Evaluation of Polymer-coated Magnetic Nanoparticles for Selective Binding of Endocrine Disrupting Compounds and Pharmaceuticals in Water by Aromatic Interactions Prepared by Musharraf Miah Department of Chemistry Carleton University September 12, 2012
Some Abbreviations CE-UV Capillary electrophoresis with ultra-violet detector EDCs Endocrine disrupting compounds PPCPs Pharmaceutical and personal care products BPA Bisphenol A MF Metformin PF Phenformin NAA Naphthalene acetic acid TC Triclosan QS Quinine sulfate MNPs Magnetic nanoparticles MNPs@PPy Polypyrrole-coated magnetic nanoparticles MNPs@PDA Polydopamine-coated magnetic nanoparticles FTIR Fourier transform infrared spectroscopy SEM Scanning electron microscopy TGA Thermogravimetric analysis XRD X-ray diffraction
Outline • Introduction • Research objectives • Experimental • Results and Discussion • Conclusion • Future work • Acknowledgement
Introduction • EDCs alter the normal functions of the endocrine system in humans and animals • They mimic the body's own hormones and lead to negative health effects • BPA is widely used in plastics (toxic) • NAA is a plant hormone used in plant rooting horticultural products, pesticides on fruits and vegetables (also toxic) • TC is used in soaps, toothpastes, detergents, hand sanitizers, mouth and dish washes
Introduction(continue) • PPCPs- wide class of chemical contaminants originate from human usage and veterinary applications • Three PPCPs analyzed MF, PF, and QS • Long-term exposure to low levels of PPCP residues could have adverse effects on aquatic ecosystem and human health (Environment Canada) • EDCs and PPCPs are found in aquatic environment from sewage treatment plant effluent, agricultural runoff, concentrated animal feed, landfill leachates, and urban runoff
Introduction(continue) • MNPs are currently attracting a wide range of applications in water treatment (not target selective in complex water matrices) • Target selective MNPs MNPs@PDA, MNPs@PPy
Chemical structures of target compounds MF BPA PF NAA TC QS
Researchobjectives • Synthesize MNPs, MNPs@PDA and MNPs@PPy nanoparicles • Characterize the particles by FTIR, SEM, TGA and XRD • Evaluate these magnetic nanoparticles for selective binding with BPA, NAA, MF, PF, TC, and QS in water by CE-UV • Study the adsorption kinetics and adsorption isotherms of BPA, TC and PF • Utilize these particles as magnetic sorbents for the preconcentration of target compounds in water analysis
Experimental • Experimental setup for coating MNPs with PPy or PDA • Illustration ofFe3O4 and Fe3O4@PPy syntheses Ref: X. Wang, L. Wang, X. He, Y. Zhang and L. Chen, Talanta. 2009, 78, 327-332. J. Meng, J. Bu, C. Deng and X. Zhang, J. Chromatogr. A., 2011, 1218, 1585-1591 H. Z. Wen, H. L. Chun, C. G. Xiu, R. C. Fa, H. Y. Huang, and R. W. Xiao, J. Mater. Chem., 2010, 20, 880-883
FTIR spectra of MNPs, PPy and MNPs@PPy particles Ref: T. Yao, T. Cui, J. Wu, Q. Chen, S. Lu, and K. Sun, Polymer chemistry, 2011, 2, 2893 Y. Wang, W. Chen, D. Zhou and G. Xue, Macromol. Chem. Phys., 2009, 210, 936-941.
FTIR spectra of MNPs and MNPs@PDA particles Ref: L. P. Zhu, J. H. Jiang, B. K. Zhu, and Y.Y. Xu, Colloid. Surface. B., 2011, 86, 111-118.
SEM images of MNPs, MNPs@PPy • Average MNPs = 45-50 nm, MNPs@PPy = 70-75 nm, MNPs@PDA = 75-80 nm • PPy coating = 12-15 nm, PDA coating = 15-18 nm
XRD spectra of MNPs and MNPs@PPy particles • Characteristic peaks for MNPs: 31.7°, 37.1°, 44.8°, 55.3°, 58.9° and 64.4° • New peaks for MNPs@PPy: 14.6 ° and 22 ° Ref: A. Hrdina, E.P.C. Lai, C.S. Li, B. Sadi and G. Kramer, J. Magn. Magn. Mater., 2010, 322, 2622-2627. T. Yao, T. Cui, J. Wu, Q. Chen, S. Lu, and K. Sun, Polymer chemistry, 2011, 2, 2893.
Capillary electrophoresis Capillary Background electrolyte (BGE)
Results and Discussions Electrophoretic mobility values of analytes, MNPs, MNPs@PDA and MNPs@PPy Mep = Mapp – Meo = [(Ld/ t) / (V/ Lt)] - [(Ld/ t neutral) / V/Lt)]
CE-UV electropherogram for a mixture of BPA, MF, NAA, PF, TC, and QS (200 µg.mL-1) in 20 mM Na2HPO4 BGE
Electropherograms of Standard BPA, PF, TC and NAA 4 mAU detector signal 2 mAU detector signal 2 mAU detector signal 2 mAU detector signal
In-capillary binding test Electropherograms: Binding of BPA, PF, TC and NAA with MNPs@PPy
Binding selectivity (in-vitro binding test) (A) 6 analytes mixture (B) Supernatant after extraction with MNPs (C) Supernatant after extraction with MNPs@PDA (D) Supernatant after extraction with MNPs@PPy 19
Elution test of MNPs@PPy particles • A mixture of EtAc and MeOH (75:25, v/v) was selected as the eluting solvent • The % recoveries of the bound analytes were found to be 85±13% MF, 87±13% PF, 54±11% BPA, 52 ± 10% QS, 39 ±11% TC, and 37 ± 10% NAA Ref: J. Meng, J. Bu, C. Deng and X. Zhang, J. Chromatogr. A., 2011, 1218, 1585-1591.
Regeneration of MNPs@PPy particles • % Binding = 94±3% • % Recovery = 53±4%
Conclusion • High % binding (99 ± 1%) of MNPs@PPy with BPA, PF, TC, and QS were found due to π-π and hydrogen bonding interactions between PPy and analytes • Compared with unmodified MNPs, and MNPs@PDA, MNPs@PPy showed higher binding efficiency towards aromatic compounds as confirmed by in-capillary and in-vitro binding tests. • Using EtAc and MeOH (75:25,v/v) as eluting solvent , the % recoveries of target compounds are found to be between 87% and 37%
Conclusion (continue) • The higher adsorption capacity (Xm) of MNPs@PPy particles was obtained for BPA, PF, and TC • Demonstrating strong affinity and better performance of MNPs@PPy particles as adsorbents for efficient removal of these target compounds • The new coating of PPy on the used particles proved to be time saving and cost effective in recycling the used particles
Future work Chemical structures of common anticancer drugs • Investigate the binding interaction of these drugs with MNPs@PPy particles by CE-UV • The loaded particles can be used for specific drug delivery to target cancer cells
Acknowledgements • I would like to express my deepest appreciation to my supervisor, Dr. Edward Lai for his supervision, advice and guidance • I am thankful to Dr. Zafar Iqbal for his kind assistance during this study • I am thankful to all colleagues in my group for sharing their experience and knowledge • I am thankful to Anita Chun and Dr. Wendy Hao for their technical assistance • Financial support from NSERC Canada is gratefully acknowledged.