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

1

Some Abbreviations

2

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

3

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

4

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

5

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

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Chemical structures of target compounds

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BPA MF

NAA PF

TC QS

Polypyrrole and polydopamine

8

Research objectives

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

9

Experimental

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Experimental setup for coating MNPs with PPy or PDA

Illustration of Fe3O4 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

11Ref: 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

12Ref: 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

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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

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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

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Capillary

C a tio ns Ne utra ls Anio ns

Background electrolyte (BGE)

Results and Discussions

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Electrophoretic mobility values of analytes, MNPs, MNPs@PDA and MNPs@PPy

Mep = Mapp – Meo = [(Ld/ t) / (V/ Lt)] - [(Ld/ t neutral) / V/Lt)]

Migration Time

(t in min)

Molecular Weight

(g.mol-1)

Electrophoretic Mobility

(m2V-1s-1)

Metformin (MF) 3.4 ± 0.1 165.62 1.18x10-8

Phenformin (PF) 3.7 ± 0.1 205.26 6.94x10-9

Quinine sulfate (QS) 4.0 ± 0.1 782.96 2.78x10-9

Mesityl Oxide (MO) 4.2 ± 0.1 98.14 00

Bisphenol A (BPA) 4.5 ± 0.1 228.29 -2.91x10-9

Triclosan (TC) 5.5 ± 0.1 289.54 -1.12x10-8

Naphthalene acetic acid (NAA)

6.9 ± 0.1 186.20 -1.87x10-8

MNPs 7.8 ± 0.1 231.54 -2.21x10-8

MNPs@PDA 8.2 ± 0.1 ----- -2.34x10-8

MNPs@PPy 8.6 ± 0.1 ----- -2.46x10-8

CE-UV electropherogram for a mixture of BPA, MF, NAA, PF, TC, and QS (200 µg.mL-1) in 20 mM Na2HPO4 BGE

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In-capillary binding test results

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Analytes (200 µg.mL-

1)

% Binding with MNPs (10 mg. mL-1)

% Binding with MNPs@PDA (10 mg.

mL-1)

% Binding with MNPs@PPy (10 mg.

mL-1)

Bisphenol A (BPA)

5 ± 3 65 ± 5 99 ± 1

Metformin (MF)

2 ± 2 14 ± 6 34 ± 4

Naphthalene acetic acid

(NAA)

7 ± 3 21 ± 4 39 ± 6

Phenformin (PF)

5 ± 3 99 ± 1 99 ± 1

Triclosan

(TC)

6 ± 3 92 ± 3 99 ± 1

Quinine sulfate (QS)

8 ± 2 94 ± 2 98 ± 2

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4 m

AU

det

ecto

r si

gnal

2 m

AU

det

ecto

r si

gnal

2 m

AU

det

ecto

r si

gnal

2 m

AU

det

ecto

r si

gnal

Electropherograms of Standard BPA, PF, TC and NAA

In-capillary binding test

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Electropherograms: Binding of BPA, PF, TC and NAA with MNPs@PPy

In-vitro binding test results

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Analytes (200 µg. mL-1)

% Binding with MNPs (9 mg. mL-1)

% Binding with MNPs@PDA (9

mg.mL-1)

% Binding with MNPs@PPy (9

mg.mL-1)

Bisphenol A (BPA) 10 ± 3 71 ± 5 94 ± 2

Metformin (MF) 5 ± 2 43 ± 3 30 ± 4

Naphthalene acetic acid (NAA)

8 ± 2 22 ± 2 68 ± 4

Phenformin (PF) 6 ± 3 94 ± 2 99 ± 1

Triclosan (TC) 7 ± 3 95 ± 1 99 ± 1

Quinine sulfate (QS) 10 ± 2 95 ± 1 99 ± 1

(A) 6 analytes mixture (B) Supernatant after extraction with MNPs

(C) Supernatant after extraction with MNPs@PDA

(D) Supernatant after extraction with MNPs@PPy

Binding selectivity (in-vitro binding test)

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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

23Ref: J. Meng, J. Bu, C. Deng and X. Zhang, J. Chromatogr. A., 2011, 1218, 1585-1591.

Regeneration of MNPs@PPy particles

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% 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%

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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

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Future work

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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

Chemical structures of common anticancer drugs

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.

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Thank you for listening